AU2011226220B2 - Polyamides resistant to hot ageing - Google Patents

Polyamides resistant to hot ageing Download PDF

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AU2011226220B2
AU2011226220B2 AU2011226220A AU2011226220A AU2011226220B2 AU 2011226220 B2 AU2011226220 B2 AU 2011226220B2 AU 2011226220 A AU2011226220 A AU 2011226220A AU 2011226220 A AU2011226220 A AU 2011226220A AU 2011226220 B2 AU2011226220 B2 AU 2011226220B2
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alkylene
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Martin Baumert
Maxim Peretolchin
Manoranjan Prusty
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BASF SE
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06Polyamides derived from polyamines and polycarboxylic acids
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    • C08L77/00Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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    • C08G73/00Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0622Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0638Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
    • C08G73/0644Poly(1,3,5)triazines
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    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08L101/00Compositions of unspecified macromolecular compounds
    • C08L101/005Dendritic macromolecules
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    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00Characterised by the use of unspecified polymers
    • C08J2300/22Thermoplastic resins
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    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
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    • C08L2666/00Composition 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
    • C08L2666/02Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/14Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
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    • C08L2666/00Composition 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
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    • C08L2666/14Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
    • C08L2666/20Macromolecular compounds having nitrogen in the main chain according to C08L75/00 - C08L79/00; Derivatives thereof
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    • C08L61/00Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
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    • C08L79/00Compositions 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
    • C08L79/04Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors

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Abstract

Thermoplastic moulding compositions containing A) from 10 to 98% by weight of a thermoplastic polyamide, B) from 0.01 to 20% by weight of a highly branched melamine polymer or melamine-urea polymer or mixtures thereof, C) from 0 to 70% by weight of further additives, where the sum of the percentages by weight of the components A) to C) is 100%.

Description

1 Polyamides resistant to hot ageing Description 5 The invention relates to thermoplastic molding compositions, comprising A) from 10 to 98% by weight of a thermoplastic polyamide, B) from 0.01 to 20% by weight of a highly branched melamine polymer or melamine-urea polymer, or a mixture of these, 10 C) from 0 to 70% by weight of further additives, where the total of the percentages by weight of components A) to C) is 100%. The invention further relates to the use of the molding compositions of the invention for 15 producing fibers, foils, and moldings of any type, and also to the resultant moldings. Thermoplastic polyamides, such as PA6 and PA66, are often used in the form of glassfiber-reinforced molding compositions as materials in the design of components which during their lifetime have exposure to elevated temperatures, with 20 thermooxidative degradation. Although the thermooxidative degradation can be delayed by adding known heat stabilizers, it cannot be prevented in the long term, and becomes apparent by way of example in a reduced level of mechanical properties. It is highly desirable to improve the heat-aging resistance (HAR) of polyamides, since this can achieve longer lifetimes for components subject to thermal stress, or can reduce 25 the risk that these fail. As an alternative, improved HAR can also permit the use of the components at higher temperatures. WO 2006/074912 and WO 2005/007727 disclose the use of elemental iron powder in polyamides. 30 EP-A 1 846 506 discloses a combination of Cu-containing stabilizers with iron oxides for polyamides. The heat-aging resistance of the known molding compositions remains unsatisfactory, 35 in particular over prolonged periods of exposure to heat. Highly branched melamine polymers and, respectively, melamine-urea polymers are produced by way of example by the processes of WO 2000/17171, WO 2009/080787, WO 2009/27186, WO 2008/148766, and EP-A 240 867. 40 These are usually used as adhesion promoters, thixotropy additives, rheology additives, or surface modifiers, and as components for producing varnishes, coatings, adhesives, sealing compositions, casting elastomers, or foams.
2 It was therefore an object of the present invention to provide thermoplastic polyamide molding compositions which have improved HAR, and which, after heat-aging, have a good surface, and also good mechanical properties. 5 Accordingly, the molding compositions defined in the introduction have been found. The dependent claims give preferred embodiments. The molding compositions of the invention comprise, as component A), from 10 to 98% by weight, preferably from 20 to 94.9% by weight, and in particular from 25 to 89% by 10 weight, of at least one polyamide. The polyamides of the molding compositions of the invention generally have an intrinsic viscosity of from 90 to 350 ml/g, preferably from 110 to 240 ml/g, determined in a 0.5% strength by weight solution in 96% strength by weight sulfuric acid at 250C to ISO 307. 15 Preference is given to semicrystalline or amorphous resins with a molecular weight (weight average) of at least 5000, described by way of example in the following US 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. 20 Examples of these are polyamides that 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. 25 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. Merely as examples, those that may be mentioned here are adipic acid, azelaic acid, sebacic acid, dodecanedioic acid and terephthalic and/or isophthalic acid. 30 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, where the molar ratio of MXDA to adipic acid is 1:1), di(4-aminophenyl)methane, di(4-aminocyclohexyl)methane, 2,2-di(4-aminophenyl)propane, 2,2-di(4 aminocyclohexyl)propane, and 1,5-diamino-2-methylpentane. 35 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@ C31 from BASF SE). 40 Other suitable polyamides are obtainable from w-aminoalkylnitriles, e.g. aminocapronitrile (PA 6) and adipodinitrile with hexamethylenediamine (PA 66) via 3 what is known as direct polymerization in the presence of water, for example as described in DE-A 10313681, EP-A 1198491 and EP 922065. Mention may also be made of polyamides obtainable, by way of example, via 5 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. Other suitable examples are polyamides obtainable via copolymerization of two or 10 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, in particular nylon-6/6,6 copolyamides. Other copolyamides which have proven particularly advantageous are semiaromatic 15 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). Other polyamides resistant to high temperatures are known from EP-A 19 94 075 (PA 6T/61/MXD6). 20 The processes described in EP-A 129 195 and 129 196 can be used to prepare the preferred semiaromatic copolyamides with low triamine content. 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 25 comprised: AB polymers: PA 4 Pyrrolidone PA 6 E-Caprolactam 30 PA 7 Ethanolactam PA 8 Caprylolactam PA 9 9-Aminopelargonic acid PA 11 11-Aminoundecanoic acid PA 12 Laurolactam 35 AA/BB polymers: PA 46 Tetramethylenediamine, adipic acid PA 66 Hexamethylenediamine, adipic acid PA 69 Hexamethylenediamine, azelaic acid PA 610 Hexamethylenediamine, sebacic acid 40 PA 612 Hexamethylenediamine, decanedicarboxylic acid PA 613 Hexamethylenediamine, undecanedicarboxylic acid PA 1212 1,12-Dodecanediamine, decanedicarboxylic acid 4 PA 1313 1,1 3-Diaminotridecane, undecanedicarboxylic acid PA 6T Hexamethylenediamine, terephthalic acid PA MXD6 m-Xylylenediamine, adipic acid AA/BB polymers: 5 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) 10 PA 66/6/610 (see PA 66, PA 6 and PA 610) PA 61/6T (see PA 61 and PA 6T) PA PACM 12 Diaminodicyclohexylmethane, laurolactam PA 61/6T/PACM as PA 61/6T + diaminodicyclohexylmethane PA 12/MACMI Laurolactam, dimethyldiaminodicyclohexylmethane, isophthalic acid 15 PA 12/MACMT Laurolactam, dimethyldiaminodicyclohexylmethane, terephthalic acid PA PDA-T Phenylenediamine, terephthalic acid The molding compositions of the invention comprise, as component B), from 0.01 to 20% by weight, preferably from 0.1 to 5% by weight, and in particular from 0.1 to 2% by 20 weight, of a highly branched melamine polymer or melamine-urea polymer, or a mixture of these. For the purposes of the present invention, highly branched polymers B) are macromolecules which have both structural and molecular nonuniformity. As a function 25 of the conduct of the reaction, they can firstly have a structure based on a central molecule by analogy with dendrimers, but with nonuniform chain length of the branches. Secondly, they can also be based on linear molecules and have a structure that uses branched functional pendent groups. For the purposes of the present invention, "highly branched" also means that the degree of branching (DB) is from 10 to 30 99.9%, preferably from 20 to 99%, and in particular from 20 to 95%. The degree of branching is the average number of dendritic linkages plus the average number of end groups per molecule, divided by the total of the average number of dendritic linkages, the average number of linear linkages, and the average number of end groups, multiplied by 100. "Dendritic" in this context means that the degree of branching at this 35 site within the molecule is from 99.9 to 100%. Reference is also made to H. Frey et al., Acta. Polym. 1997, 48, 30 for the definition of the degree of branching. "In essence not crosslinked" or "uncrosslinked" means, within the meaning of the present invention, that the degree of branching of component B) is less than 15% by 40 weight, preferably less than 10% by weight, where the degree of branching is determined by way of the insoluble content of the polymer.
5 The insoluble content of the polymer B) is by way of example determined via extraction for 4 hours in a Soxhlet apparatus using a solvent identical with that used for the gel permeation chromatography (GPC) process, i.e. preferably dimethylacetamide or hexafluoroisopropanol, depending on which of the solvents is a better solvent for the 5 polymer B), and weighing the residue after it has been dried to constant weight. The number-average molar mass Mn of the polymers B) of the invention is preferably from 1000 to 40 000 g/mol, particularly preferably from 1500 to 30 000 g/mol, and in particular from 2000 to 20 000 g/mol. The weight-average molecular weight M, is 10 preferably from 1500 to 150 000, particularly preferably at most 100 000, more preferably at most 60 000, and in particular at most 40 000. Polydispersity (PD = quotient calculated from Mw and Mn) is preferably at least 1.1, particularly preferably at least 1.5, and in particular at least 2. 15 The molecular weight and molar mass data (Mn, Mw) and polydispersity data provided for the purposes of the present invention are based on values obtained using gel permeation chromatography (GPC) in hexafluoroisopropanol as solvent, with PMMA calibration. 20 The amine number of component B) is preferably from 100 to 900 mg KOH/g, in particular from 200 to 800 mg KOH/g, and very particularly from 300 to 700 mg KOH/g (DIN 53176). Component B) of the invention is obtainable by the processes of WO 2009/080787, via 25 reaction of (i) urea and/or at least one urea derivative; (ii) melamine; and (iii) at least one amine, where the at least one amine comprises 30 (iii.1) from 20 to 100 mol%, based on the total amount of components (iii.1), (iii.2), and (iii.3), of at least one diamine or polyamine having two primary - amino groups, (iii.2) from 0 to 50 mol%, based on the total amount of components (iii.1), (iii.2), and (iii.3), of at least one polyamine having at feast three primary amino 35 groups; and (iii.3) from 0 to 80 mol%, based on the total amount of components (iii.1), (iii.2), and (iii.3), of at least one amine having a primary amino group; and (iv) optionally at least one melamine derivative, selected from benzoguanamine, substituted melamines, and melamine condensates. 40 If melamine polymers are used as component B), these can equally be produced with optional omission of component (i), the starting materials therefore being identical 6 except that component (i) is absent. Unless otherwise stated, the following general definitions apply for the purposes of the present invention: 5
C
1
-C
4 -Alkyl is a linear or branched alkyl radical having from 1 to 4 carbon atoms. These are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, and tert-butyl. Linear C-C 4 -alkyl is a linear alkyl radical having from 1 to 4 carbon atoms. These are 10 methyl, ethyl, n-propyl, and n-butyl. Ce-C 12 -Alkyl is a linear or branched alkyl radical having from 1 to 12 carbon atoms. Examples of these are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, 15 2-propylheptyl, 4-methyl-2-propylhexyl, undecyl, dodecyl, and structural isomers of these. Aryl is a carbocyclic aromatic radical having from 6 to 14 carbon atoms, e.g. phenyl, naphthyl, anthracenyl, or phenanthrenyl. Aryl is preferably phenyl or naphthyl, and in 20 particular phenyl. Aryl-Cr-C 4 -alkyl is Cr-C 4 -alkyl as defined above, but where a hydrogen atom has been replaced by an aryl group. Examples are benzyl, phenethyl, and the like. 25 Cr1C4-Alkylene is a linear or branched divalent alkyl radical having 1, 2, 3, or 4 carbon atoms. Examples are -CH 2 -, -CH 2
CH
2 -, -CH(CH 3 )-, -CH 2
CH
2
CH
2 -, -CH(CH 3
)CH
2 -, CH 2
CH(CH
3 )-, -C(CH 3
)
2 -, -CH 2
CH
2
CH
2
CH
2 -, -CH(CH 3
)CH
2
CH
2 -, -CH 2
CH
2
CH(CH
3 )-, C(CH 3 ) 2
CH
2 -, -CH 2
C(CH
3
)
2 -, and -CH 2
CH
2
CH
2
CH
2
CH
2 -. 30 Linear or branched C2-C5-alkylene is a linear or branched divalent alkyl radical having 2, 3, 4, or 5 carbon atoms. Examples are -CH 2
CH
2 -, -CH(CH 3 )-, -CH 2
CH
2
CH
2 -,
-CH(CH
3
)CH
2 -, -CH 2
CH(CH
3 )-, -C(CH 3
)
2 -, -CH 2
CH
2
CH
2
CH
2 -, -CH(CH 3
)CH
2
CH
2 -,
-CH
2
CH
2
CH(CH
3 )-, -C(CH 3 ) 2
CH
2 -, -CH 2
C(CH
3
)
2 -, and -CH 2
CH
2
CH
2
CH
2
CH
2 -. 35 Linear or branched C4-C8-alkylene is a linear or branched divalent alkyl radical having from 4 to 8 carbon atoms. Examples are -CH 2
CH
2
CH
2
CH
2 -, -CH(CH 3
)CH
2
CH
2 -,
-CH
2
CH
2
CH(CH
3 )-, -C(CH 3
)
2
CH
2 -, -CH 2
C(CH
3
)
2 -, -CH 2
CH
2
CH
2
CH
2
CH
2 -,
-CH
2
C(CH
3
)
2
CH
2 -, -CH 2
CH
2
CH
2
CH
2
CH
2
CH
2 -, -(CH 2
)
7 -, -(CH 2
)
8 -, and positional isomers thereof. 40 Linear or branched C2-Clo-alkylene is a linear or branched divalent alkyl radical having from 2 to 10 carbon atoms. Examples, alongside the abovementioned C2-C5-alkylene 7 radicals, are the higher homologs having from 6 to 10 carbon atoms, e.g. hexylene, heptylene, octylene, nonylene, and decylene. Linear or branched C2-C2-alkylene is a linear or branched divalent alkyl radical having 5 from 2 to 20 carbon atoms. Examples, alongside the abovementioned C2-C 5 -alkylene radicals, are the higher homologs having from 6 to 20 carbon atoms, e.g. hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, heptadecylene, octadecylene, nonadecylene, and eicosylene. 10 Alkenylene is a linear or branched aliphatic mono- or polyolefinically unsaturated, e.g. mono- or diolefinically unsaturated, divalent radical having by way of example from 2 to 20, or from 2 to 10, or from 4 to 8, carbon atoms. If the radical comprises more than one carbon-carbon double bond, these are preferably not vicinal, i.e. not allenic. 15 Alkynylene is a linear or branched aliphatic divalent radical having by way of example from 2 to 20, or from 2 to 10, or from 4 to 8, carbon atoms, and comprising one or more, e.g. 1 or 2, carbon-carbon triple bonds. 20 C5-C8-Cycloalkylene is a divalent monocyclic, saturated hydrocarbon group having from 5 to 8 carbon ring members. Examples are cyclopentane-1,2-diyl, cyclopentane 1,3-diyl, cyclohexane-1,2-diyl, cyclohexane-1,3-diyl, cyclohexane-1,4-diyl, cycloheptane-1,2-diyl, cycloheptane-1,3-diyl, cycloheptane-1,4-diyl, cyclooctane 1,2-diyl, cyclooctane-1,3-diyl, cyclooctane-1,4-diyl, and cyclooctane-1,5-diyl. 25 A 5- or 6-membered unsaturated nonaromatic heterocycle which has bonding by way of N and which can also comprise one or two further nitrogen atoms, or one further sulfur atom or oxygen atom, as ring member, is by way of example pyrrolin-1-yl, pyrazolin-1-yl, imidazolin-1-yl, 2,3-dihydrooxazol-3-yl, 2,3-, and 2,5-dihydroisoxazol-2 30 yl, 2,3-dihydrothiazol-3-yl, 2,3-, and 2,5-dihydroisothiazol-2-yl, [1,2,3]-1 H-triazolin-1 -yl, [1,2,4]-1 H-triazolin-1 -yl, [1,3,4]-1 H-triazolin-1 -yl, [1,2,3]-2H-triazolin-2-y, 1,2 dihydropyridin-1-yl, 1,4-dihydropyridin-1-yl, 1,2,3,4-tetrahydropyridin-1-yl, 1,2 dihydropyridazin-1-yl, 1,4-dihydropyridazin-1-yl, 1,6-dihydropyridazin-1-yl, 1,2,3,4 tetrahydropyridazin-1 -yl, 1,4,5,6-tetrahydropyridazin-1-yl, 1,2-dihydropyrimidin-1-yl, 1,4 35 dihydropyrimidin-1-yl, 1,6-dihydropyrimidin-1-yl, 1,2,3,4-tetrahydropyrimidin-1-yl, 1,4,5,6-tetrahydropyrimidin-1-yl, 1,2-dihydropyrazin-1-yl, 1,4-dihydropyrazin-1-yl, 1,2,3,4-tetrahydropyrazin-1-yl,1,4-oxazin-4-yl, 2,3-dihydro-1,4-oxazin-4-yl, 2,3,5,6 tetrahydro-1,4-oxazin-4-yl, 1,4-thiazin-4-yl, 2,3-dihydro-1,4-thiazin-4-yl, 2,3,5,6 tetrahydro-1 ,4-thiazin-4-yl, 1,2-dihydro-1,3,5-triazin-1-yl, 1,2,3,4-tetrahydro-1,3,5 40 triazin-1-yl, and the like. A 5- or 6-membered unsaturated aromatic heterocycle which has bonding by way of N 8 and which can also comprise a further nitrogen atom, as ring member, is by way of example pyrrol-1-yl, pyrazol-1-yl, imidazol-1-yl, and triazol-1-yl. A primary amino group is an -NH 2 radical. 5 The statements made below relating to preferred embodiments of the process of the invention, in particular relating to the monomers and further reaction components used in the invention, and to the polymers obtainable by the process, and also to the use of these, apply either in isolation or in particular in any conceivable combination. 10 Urea and/or a urea derivative is usually used as component (i). It is preferable that the urea derivatives have been selected from 15 - substituted ureas of the formula R 1
R
2 N-C(=O)-NR3R4, in which R 1 , R 2 , R 3 and R 4 , independently of one another, have been selected from hydrogen, C-C 12 -alkyl, aryl, and aryl-C-C 4 -alkyl, or R1 and R 2 and/or R 3 and R 4 respectively together are C2-C5-alkylene, where a methylene group (i.e. a CH 2 group in the alkylene chain) can optionally have 20 been replaced by a carbonyl group, or R 1 and R 3 together are C2-C5-alkylene, where a methylene group (i.e. a CH 2 group in the alkylene chain) can optionally have been replaced by a carbonyl group, or R 1 and R 2 , and/or R 3 and R 4 , respectively together with the nitrogen atom 25 bonded thereto, form a 5- or 6-membered unsaturated aromatic or nonaromatic ring, which can comprise one or two further nitrogen atoms, or a sulfur atom or oxygen atom, as ring member (i.e. R 1 and R 2 and, respectively, R 3 and R 4 , together with the nitrogen atom bonded thereto, are a 5- or 6-membered unsaturated aromatic or nonaromatic ring which has bonding by way of N and 30 which can comprise one or two further nitrogen atoms, or a sulfur atom or oxygen atom, as ring member); where at least one of the radicals R 1 , R 2 , R 3 , and R 4 is not hydrogen; - thiourea; 35 - substituted thioureas of the formula RSR 6
N-C(=S)-NR
7 R8, in which R 5 , R 6 , R 7 , and
R
8 , independently of one another, have been selected from hydrogen, CrC-12 alkyl, aryl, and aryl-C1-C4-alkyl, or R 5 and R 6 and/or R 7 and R 8 respectively together are C2-C5-alkylene, where a 40 methylene group (i.e. a CH 2 group in the alkylene chain) can optionally have been replaced by a carbonyl group, or R 5 and R 7 together are C2-CS-alkylene, where a methylene group (i.e. a CH 2 9 group in the alkylene chain) can optionally have been replaced by a carbonyl group, or R 5 and R 6 , and/or R 7 and R 8 , respectively together with the nitrogen atom bonded thereto, form a 5- or 6-membered unsaturated aromatic or nonaromatic 5 ring, which can comprise one or two further nitrogen atoms, or a sulfur atom or oxygen atom, as ring member (i.e. R 5 and R 6 and, respectively, R 7 and R 8 , together with the nitrogen atom bonded thereto, are a 5- or 6-membered unsaturated aromatic or nonaromatic ring which has bonding by way of N and which can comprise one or two further nitrogen atoms, or a sulfur atom or oxygen 10 atom, as ring member); where at least one of the radicals R 5 , R 6 , R 7 , and R 8 is not hydrogen; - guanidine; 15 - substituted guanidines of the formula R 9 R1ON-C(=NR11)-NR12R13, in which R 9 , RIO,
R
11 , R 1 2 , and R 13 , independently of one another, have been selected from hydrogen, C1-C12-alkyl, aryl, and aryl-C1-C 4 -alkyl, or R 9 and RIO and/or R 12 and R 13 respectively together are C2-C5-alkylene, where a methylene group (i.e. a CH 2 group in the alkylene chain) can optionally have 20 been replaced by a carbonyl group, or R 9 and R 12 together are C2-CS-alkylene, where a methylene group (i.e. a CH 2 group in the alkylene chain) can optionally have been replaced by a carbonyl group, or R 9 and R 1 0 , and/or R 12 and R' 3 , respectively together with the nitrogen atom 25 bonded thereto, form a 5- or 6-membered unsaturated aromatic or nonaromatic ring, which can also comprise a further nitrogen atom, sulfur atom or oxygen atom, as ring member (i.e. R 9 and R 1 0 and, respectively, R 12 and R 13 , together with the nitrogen atom bonded thereto, are a 5- or 6-membered unsaturated aromatic or nonaromatic ring which has bonding by way of N and which can 30 comprise one or two further nitrogen atoms, or a sulfur atom or oxygen atom, as ring member); where at least one of the radicals R 9 , R 10 , R 11 , R 1 2 , and R 13 is not hydrogen; and - carbonic esters of the formula R14-O-CO-O-R15, in which R 14 and R 15 , 35 independently of one another, have been selected from C1-C 1 2 -alkyl, aryl, and aryl-C-C 4 -alkyl, or R 14 and R 1 5 together are C2-Cs-alkylene. It is, of course, also possible to use mixtures of various urea derivatives. 40 In a preferred embodiment, R 2 and R 4 in the substituted ureas are hydrogen, and R 1 and R 3 are identical or different and are Cl-C 1 2 -alkyl, aryl, or aryl-C-C 4 -alkyl. Examples here are N,N'-dimethylurea, N,N'-diethylurea, N,N'-dipropylurea, N,N'-diisopropylurea, 10 N,N'-di-n-butylurea, N,N'-diisobutylurea, N,N'-di-sec-butylurea, N,N'-di-tert-butylurea, N,N'-dipentylurea, N,N'-dihexylurea, N,N'-diheptylurea, N,N'-dioctylurea, N,N'-didecylurea, N,N'-didodecylurea, N,N'-diphenylurea, N,N'-dinaphthylurea, N,N'-ditolylurea, N,N'-dibenzylurea, N-methyl-N'-phenylurea, and N-ethyl 5 N'-phenylurea. In an alternatively preferred embodiment, R 1 , R 2 , R 3 , and R 4 are identical and are linear
C
1
-C
4 -alkyl. Examples here are N,N,N',N'-tetramethylurea and N,N,N',N'-tetraethylurea. 10 In an alternatively preferred embodiment, R 1 and R 2 , and also R 3 and R 4 , are respectively together C2-C 5 -alkylene; that means that R 1 and R 2 together form a C 2
-C
5 alkylene group and that R 3 and R 4 together form a C2-C 5 -alkylene group. Examples here are di(tetrahydro-1 H-pyrrol-1 -yl)methanone, bis(pentanethylene)urea, and carbonylbiscaprolactam. 15 In an alternatively preferred embodiment, R 2 and R 4 are hydrogen, and R1 and R 3 together form a C2-C5-alkylene group, where a methylene group can optionally have been replaced by a carbonyl group. Examples here are ethyleneurea, and also 1,2- or 1,3-propyleneurea. 20 In an alternatively preferred embodiment, R1 and R 2 , and also R 3 and R 4 , respectively form, together with the nitrogen atom bonded thereto, an unsaturated aromatic or nonaromatic heterocycle as defined above. Examples here are carbonyldipyrazole and carbonyldiimidazole. 25 In a preferred embodiment, R 6 and R 8 in the substituted thioureas are hydrogen, and
R
5 and R 7 are identical or different and are C-C 1 2 -alkyl, aryl, or aryl-C-C 4 -alkyl. Examples here are N,N'-dimethylthiourea, N,N'-diethylthiourea, N,N'-dipropylthiourea, N,N'-diisopropylthiourea, N,N'-di-n-butylthiourea, N,N'-diisobutylthiourea, N,N'-di-sec 30 butylthiourea, N,N'-di-tert-butylthiourea, N,N'-dipentylthiourea, N,N'-dihexylthiourea, N,N'-diheptylthiourea, N,N'-dioctylthiourea, N,N'-didecylthiourea, N,N' didodecylthiourea, N,N'-diphenylthiourea, N,N'-dinaphthylthiourea, N,N'-ditolylthiourea, N,N'-dibenzylthiourea, N-methyl-N'-phenylthiourea, and N-ethyl-N'-phenylthiourea. 35 In an alternatively preferred embodiment, R 5 , R 6 , R 7 , and R 8 are identical and are linear
C-C
4 -alkyl. Examples here are N,N,N',N'-tetramethylthiourea and N,N,N',N' tetraethylthiourea. In an alternatively preferred embodiment, R 5 and R 6 , and also R 7 and R 8 , respectively 40 are together C2-CS-alkylene; that means that R 5 and R 6 together form a C2-CS-alkylene group, and that R 7 and R 8 together form a C2-CS-alkylene group. Examples here are di(tetrahydro-1 H-pyrrol-1 -yl)methanethione, bis(pentamethylene)thiourea, and 11 thiocarbonylbiscaprolactam. In an alternatively preferred embodiment, R 6 and R 8 are hydrogen, and R 5 and R 7 together form a C2-C 5 -alkylene group, where a methylene group can optionally have 5 been replaced by a thiocarbonyl group. Examples here are ethylenethiourea, and also 1,2- or 1,3-propylenethiourea. In an alternatively preferred embodiment, R 5 and R 6 , and also R 7 and R 8 , respectively form, together with the nitrogen atom bonded thereto, an unsaturated aromatic or 10 nonaromatic heterocycle as defined above. Examples here are thiocarbonyldipyrazole and thiocarbonyldiimidazole. In a preferred embodiment, R 1 0 and R 13 in the substituted guanidines are hydrogen, and R 9 and R 12 are identical or different and are C 1
-C
1 2 -alkyl, aryl, or aryl-C 1
-C
4 -alkyl. 15 Examples here are N,N'-dimethylguanidine, N,N'-diethylguanidine, N,N'-dipropylguanidine, N,N'-diisopropylguanidine, N,N'-di-n-butylguanidine, N,N'-diisobutylguanidine, N,N'-di-sec-butylguanidine, N,N'-di-tert-butylguanidine, N,N'-dipentylguanidine, N,N'-dihexylguanidine, N,N'-diheptylguanidine, N,N'-dioctylguanidine, N,N'-didecylguanidine, N,N'-didodecylguanidine, 20 N,N'-diphenylguanidine, N,N'-dinaphthylguanidine, N,N'-ditolylguanidine, N,N'-dibenzylguanidine, N-methyl-N'-phenylguanidine, and N-ethyl-N'-phenylguanidine. In an alternatively preferred embodiment, R 9 , R 10 , R1 2 , and R 13 are identical and are linear C1-C 4 -alkyl. Examples here are N,N,N',N'-tetramethylguanidine and N,N,N',N' 25 tetraethylguanidine. In an alternatively preferred embodiment, R 9 and R 10 , and also R1 2 and R 1 3 , are respectively together C2-C 5 -alkylene; that means that R 9 and R 1 0 together form a C 2
-C
5 alkylene group and that R 12 and R 13 together form a C2-C 5 -alkylene group. Examples 30 here are di(tetrahydro-1H-pyrrol-1-yl)imine, bis(pentamethylene)guanidine, and iminobiscaprolactam. In an alternatively preferred embodiment, R 10 and R 13 are hydrogen, and R 9 and R 12 together form a C2-C5-alkylene group, where a methylene group, can optionally have 35 been replaced by a carbonyl group. Examples here are ethyleneguanidine, and also 1,2- or 1,3-propyleneguanidine. In an alternatively preferred embodiment, R 9 and R 1 0 , and also R 12 and R 13 , respectively form, together with the nitrogen atom bonded thereto, an unsaturated 40 aromatic or nonaromatic heterocycle as defined above. Examples here are iminodipyrazole and iminodiimidazole.
12 In a preferred embodiment, R 14 and R 1 5 are C 1
-C
4 -alkyl. It is particularly preferable that the two radicals are identical. Examples here are dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, di-n-butyl carbonate, di-sec-butyl carbonate, diisobutyl carbonate, and di-tert-butyl carbonate. Among these, preference 5 is given to dimethyl carbonate and diethyl carbonate. In an alternatively preferred embodiment, R 1 4 and R 15 together are C2-C 5 -alkylene, and preferably C2-C3-alkylene. Examples of these carbonates are ethylene carbonate, and also 1,2- and 1,3-propylene carbonate. 10 Among the abovementioned urea derivatives, preference is given to the substituted ureas, thiourea, the substituted thioureas, and the carbonic esters. More preference is given to the substituted ureas, thiourea, and the carbonic esters. Among these, preference is given to thiourea, N,N'-dimethylurea, N,N'-diethylurea, N,N'-di 15 n-butylurea, N,N'-diisobutylurea, N,N,N',N'-tetramethylurea, dimethyl carbonate, diethyl carbonate, ethylene carbonate, and 1,2-propylene carbonate. However, it is preferable to use urea itself as component (i), optionally in combination with one of the abovementioned urea derivatives, and it is particularly preferable to use 20 only urea. Component (i) is not used as starting material for producing the melamine polymers. The at least one amine (iii) is preferably composed exclusively of components (iii.1), 25 (iii.2), and (iii.3); that means that the proportions of said three components give a total of 100 mol% of component (iii). The amount used of component (iii.1) is preferably from 30 to 100 mol%, particularly preferably from 50 to 100 mol%, and in particular from 75 to 100 mol%, based on the 30 total amount of components (iii.1), (iii.2), and (iii.3). The amount used of component (iii.2) is preferably from 0 to 40 mol%, particularly preferably from 0 to 30 mol%, and in particular from 0 to 15 mol%, based on the total amount of components (iii.1), (iii.2), and (iii.3). 35 The amount used of component (iii.3) is preferably from 0 to 70 mol%, particularly preferably from 0 to 50 mol%, and in particular from 0 to 25 mol%, based on the total amount of components (iii.1), (iii.2), and (iii.3). 40 If component (iii.2) is used, the amount used thereof is preferably from 1 to 50 mol%, e.g. from 5 to 50 mol% or from 10 to 50 mol%, particularly preferably from 1 to 40 mol%, e.g. from 5 to 40 mol% or from 10 to 40 mol%, more preferably from 1 to 13 30 mol%, e.g. from 5 to 30 mol% or from 10 to 30 mol%, and in particular from 1 to 15 mol%, e.g. from 2 to 15 mol% or from 5 to 15 mol%, based on the total amount of components (iii.1), (iii.2), and (iii.3). 5 If component (iii.3) is used, the amount used thereof is preferably from 1 to 80 mol%, e.g. from 5 to 80 mol% or from 10 to 80 mol%, particularly preferably from 1 to 70 mol%, e.g. from 5 to 70 mol% or from 10 to 70 mol%, more preferably from 1 to 50 mol%, e.g. from 5 to 50 mol% or from 10 to 50 mol%, and in particular from 1 to 25 mol%, e.g. from 5 to 25 mol% or from 10 to 25 mol%, based on the total amount of 10 components (iii.1), (iii.2), and (iii.3). Component (iii.1) comprises exactly two primary amino groups (-NH 2 ). If component (iii.1) is a polyamine, this comprises two primary amino groups (-NH 2 ) 15 and, in addition, one or more secondary amino groups (-NHR; R not equal to H), and/or tertiary amino groups (-NRR'; R and R' not equal to H), e.g. from 1 to 20, or from 1 to 10, or from 1 to 4, secondary and/or tertiary amino groups. If component (iii.1) is a diamine, this comprises no further amino functions other than 20 the two primary amino groups. The di- or polyamine of component (iii.1) has preferably been selected from amines of the formula 25
NH
2
-A-NH
2 in which A is a divalent aliphatic, alicyclic, aliphatic-alicyclic, aromatic, or araliphatic radical, 30 where the abovementioned radicals can also have interruption by a carbonyl group or by a sulfone group, and/or can have substitution by 1, 2, 3, or 4 radicals selected from C-C 4 -alkyl; or is a divalent radical of the formula -{B-X-B}a 35 in which X is 0 or NRa, in which Ra is H, C-C 4 -alkyl, C2-C4-hydroxyalkyl, or C 1
-C
4 alkoxy; 40 B is C2-C6-alkylene; and a is a number from 1 to 20.
14 Mixtures of said amines are also suitable. Divalent aliphatic radicals are those which do not comprise any cycloaliphatic, 5 aromatic, or heterocyclic constituents. Examples are alkylene, alkenylene, and alkynylene radicals. Divalent alicyclic radicals can comprise one or more, e.g. one or two, alicyclic radicals; however, they do not comprise any aromatic or heterocyclic constituents. The alicyclic 10 radicals can have substitution by aliphatic radicals, but the location of both of the bonding sites for the NH 2 groups is at the alicyclic radical. Divalent aliphatic-alicyclic radicals comprise not only at least one divalent aliphatic radical but also at least one divalent alicyclic radical, where the location of the two 15 bonding sites for the NH 2 groups can be as follows: either both at the alicyclic radical(s) or both at the aliphatic radical(s), or one at an aliphatic radical and the other at an alicyclic radical. Divalent aromatic radicals can comprise one or more, e.g. one or two, aromatic 20 radicals; however, they comprise no alicyclic or heterocyclic constituents. The aromatic radicals can have substitution by aliphatic radicals, but the location of both of the bonding sites for the NH 2 groups is at the aromatic radical. Divalent araliphatic radicals comprise not only at least one divalent aliphatic radical but 25 also at least one divalent aromatic radical, where the location of the two bonding sites for the NH 2 groups can be as follows: either both at the aromatic radical(s) or both at the aliphatic radical(s), or one at an aliphatic radical and the other at an aromatic radical. 30 In a preferred embodiment, the divalent aliphatic radical A is linear or branched C 2
-C
20 alkylene, particularly preferably linear or branched C2-Clo-alkylene, and in particular linear or branched C4-C 8 -alkylene. Examples of suitable amines in which the radical A is defined in this way (C 2
-C
20 35 alkylene) are 1,2-ethylenediamine, 1,2- and 1,3-propylenediamine, 2,2-dimethyl 1,3-propanediamine, 1,4-butylenediamine, 1,5-pentylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, tridecamethylenediamine, tetradecamethylenediamine, 40 pentadecamethylenediamine, hexadecamethylenediamine, heptadecamethylene diamine, octadecamethylenediamine, nonadecamethylenediamine, eicosamethylene diamine, 2-butyl-2-ethyl-1,5-pentamethylenediamine, 2,2,4- or 2,4,4-trimethyl-1,6- 15 hexamethylenediamine, 1,5-diamino-2-methylpentane, 1,4-diamino-4-methylpentane, and the like. Among these, preference is given to amines in which A is linear or branched C 2
-C
10 5 alkylene, as in 1,2-ethylenediamine, 1,2- and 1,3-propylenediamine, 2,2-dimethyl 1,3-propanediamine, 1,4-butylenediamine, 1,5-pentylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, 2,2,4- or 2,4,4-trimethyl 1,6-hexamethylenediamine, 1,5-diamino-2-methylpentane, 1,4-diamino 10 4-methylpentane, and the like. Among these, particular preference is given to amines in which A is linear or branched C4-C8-alkylene, as in 2,2-dimethyl-1,3-propanediamine, 1,4-butylenediamine, 1,5-pentylenediamine, hexamethylenediamine, heptamethylenediamine, 15 octamethylenediamine, 1,5-diamino-2-methylpentane, 1,4-diamino-4-methylpentane, and the like. In a specific embodiment, amines are used in which A is linear or branched C 4 -C8-alkylene, where at most one branching system starts from any carbon atom in the branched alkylene. Examples of these amines are 1,4-butylenediamine, 1,5-pentylenediamine, hexamethylenediamine, heptamethylenediamine, 20 octamethylenediamine, and 1,5-diamino-2-methylpentane, i.e. the amines listed above as particularly preferred except for 2,2-dimethyl-1,3-propanediamine and 1,4-diamino 4-methylpentane. Still more specifically, amines are used in which A is linear C 4
-C
8 alkylene, e.g. 1,4-butylenediamine, 1,5-pentylenediamine, hexamethylenediamine, heptamethylenediamine, and octamethylenediamine. 25 In a preferred embodiment, the divalent alicyclic radicals A have been selected from Cs-C8-cycloalkylene which can bear 1, 2, 3, or 4 C-C 4 -alkyl radicals. Examples of suitable amines in which the radical A has this definition are 30 cyclopentylenediamine, such as 1,2-diaminocyclopentane or 1,3-diaminocyclopentane, cyclohexylenediamine, such as 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, or 1,4-diaminocyclohexane, 1-methyl-2,4-diaminocyclohexane, 1-methyl 2,6-diaminocyclohexane, cycloheptylenediamine, such as 1,2-diaminocycloheptane, 1,3-diaminocycloheptane or 1,4-diaminocycloheptane, and cyclooctylenediamine, such 35 as 1,2-diaminocyclooctane, 1,3-diaminocyclooctane, 1,4-diaminocyclooctane or 1,5-diaminocyclooctane. The amino groups can have cis- or trans-position with respect to one another. In a preferred embodiment, the divalent aliphatic-alicyclic radicals A have been 40 selected from Cs-C8-cycloalkylene-C-C 4 -alkylene, CS-C8-cycloalkylene-C-C 4 -alkylene C5-C8-cycloalkylene, and C-C4-alkylene-Cs-Cs-cycloalkylene-C-C 4 -alkylene, where the cycloalkylene radicals can bear 1, 2, 3, or 4 CC4-alkyl radicals.
16 Examples of suitable amines in which the radical A has this definition are diaminodicyclohexylmethane, isophoronediamine, bis(aminomethyl)cyclohexane, such as 1,1-bis(aminomethyl)cyclohexane, 1,2-bis(aminomethyl)cyclohexane, 5 1,3-bis(aminomethyl)cyclohexane, or 1,4-bis(aminomethyl)cyclohexane, 2-aminopropylcyclohexylamine, 3(4)-aminomethyl-1-methylcyclohexylamine, and the like. The groups bonded at the alicyclic radical can assume any desired relative position (cis/trans) with respect to one another. 10 In a preferred embodiment, the divalent aromatic radicals A have been selected from phenylene, biphenylene, naphthylene, phenylene sulfone phenylene, and phenylene carbonyl phenylene, where the phenylene and naphthylene radicals can bear 1, 2, 3, or 4 C-C 4 -alkyl radicals. 15 Examples of suitable amines in which the radical A has this definition are phenylenediamine, such as o-, m-, and p-phenylenediamine, tolylenediamine, such as o-, m-, and p-tolylenediamine, xylylenediamine, naphthylenediamine, examples being 1,2-, 1,3-, 1,4-, 1,5-, 1,8-, 2,3-, 2,6-, and 2,7-naphthylene, diaminodiphenyl sulfone, examples being 2,2'-, 3,3'-, and 4,4'-diaminodiphenyl sulfone, and 20 diaminobenzophenone, examples being 2,2'-, 3,3'-, and 4,4'-diaminobenzophenone. In a preferred embodiment, the divalent araliphatic radicals A have been selected from phenylene-C-C 4 -alkylene and phenylene-Cr1C4-alkylenephenylene, where the phenylene radicals can bear 1, 2, 3, or 4 C-C 4 -alkyl radicals. 25 Examples of suitable amines in which the radical A has this definition are diaminodiphenylimethane, examples being 2,2'-, 3,3'-, and 4,4'-diaminodiphenylmethane, and the like. 30 In a preferred embodiment, X is 0, and a here is preferably a number from 2 to 6. Examples of suitable amines in which the radical A has this definition are amine terminated polyoxyalkylene polyols, examples being Jeffamines, such as 4,9-dioxadodecane-1, I 2-diamine and 4,7,1 0-trioxatridecane-1, 1 3-diamine, or else 35 amine-terminated polyoxyalkylene polyols of more regular type, examples being amine terminated polyethylene glycols, amine-terminated polypropylene glycols, or amine terminated polybutylene glycols. The molar mass of the three last-mentioned amines (amine-terminated polyalkylene glycols) is preferably from 200 to 3000 g/mol. 40 In an alternatively preferred embodiment, X is NRa. Ra here is preferably H or Cr-C4 alkyl, particularly preferably H or methyl, and in particular H. B here is in particular C2-C3-alkylene, such as 1,2-ethylene, 1,2-propylene, and 1,3-propylene, and in 17 particular 1,2-ethylene, and a is preferably a number from 1 to 10, particularly preferably from 1 to 6, and in particular from 1 to 4. Examples of suitable amines in which the radical A has this definition are 5 diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, heptaethyleneoctamine, octaethylenenonamine, higher polyimines, bis(3-aminopropyl)amine, bis(3-aminopropyl)methylamine, and the like. 10 It is preferable to use, as component (iii.1), at least one diamine having two primary amino groups. Accordingly, the at least one amine (iii.1) comprises no further (primary, secondary, and/or tertiary) amino groups alongside the two primary amino functions. Preferred diamines having two primary amino groups are those of the formula NH 2
-A
15 NH 2 , in which A is a divalent aliphatic, alicyclic, aliphatic-alicyclic, aromatic, or araliphatic radical, where the abovementioned radicals can also have interruption by a carbonyl group or by a sulfone group, and/or can have substitution by 1, 2, 3, or 4 radicals selected from C-C 4 -alkyl, and where the abovementioned radicals comprise, of course, no amino groups; or is a divalent radical of the formula 20 4B-X-B}a in which X is 0; B is C2-C6-alkylene; and a is a number from 1 to 100, preferably from 1 to 80, and in particular from I to 20. 25 The above statements relating to suitable and preferred aliphatic, alicyclic, aliphatic alicyclic, aromatic, or araliphatic radicals, and to divalent radicals of the formula -[B-X-B}a, in which X is 0, are hereby incorporated herein by way of reference, as also are the associated preferred and suitable amines. 30 Particularly preferred diamines having two primary amino groups are those of the formula NH 2
-A-NH
2 , in which A is a divalent aliphatic radical and is preferably linear or branched C2-C2o-alkylene. Examples of suitable amines in which the radical A has this definition (C2-C20-alkylene) are 1,2-ethylenediamine, 1,2- and 1, 3-propylenediamine, 35 2,2-dimethyl-1,3-propanediamine, 1,4-butylenediamine, 1,5-pentylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, tridecamethylenediamine, tetradecamethylenediamine, pentadecamethylenediamine, hexadecamethylenediamine, 40 heptadecamethylenediamine, octadecamethylenediamine, nonadecamethylenediamine, eicosamethylenediamine, 2-butyl-2-ethyl 1,5-pentamethylenediamine, 2,2,4- or 2,4,4-trimethyl-1,6-hexamethylenediamine, 18 1,5-diamino-2-methylpentane, 1,4-diamino-4-methylpentane, and the like. It is particularly preferable that A in the diamines having two primary amino groups is linear or branched C2-Clo-alkylene. Examples of suitable amines in which the radical A 5 has this definition (C2-Clo-alkylene) are 1,2-ethylenediamine, 1,2- and 1,3-propylenediamine, 2,2-dimethyl-1,3-propanediamine, 1,4-butylenediamine, 1,5-pentylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, 2,2,4- or 2,4,4-trimethyl- 1,6-hexamethylenediamine, 1,5-diamino-2-methylpentane, 1,4-diamino 10 4-methylpentane, and the like. In particular, A in the diamines having two primary amino groups is linear or branched
C
4 -C8-alkylene. Examples of suitable amines in which the radical A has this definition
(C
4 -C8-alkylene) are 2,2-dimethyl-1,3-propanediamine, 1,4-butylenediamine, 15 1,5-pentylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, 1,5-diamino-2-methylpentane, 1,4-diamino-4-methylpentane, and the like. In one specific embodiment, amines are used in which A is linear or branched C 4
-C
8 -alkylene, where at most one branching system starts from any carbon atom in the branched alkylene. Examples of these amines are 1,4-butylenediamine, 20 1,5-pentylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, and 1,5-diamino-2-methylpentane, i.e. the amines listed above as particularly preferred except for 2,2-dimethyl-1,3-propanediamine and 1,4-diamino 4-methylpentane. Among these, more preference is given to amines in which A is linear
C
4
-C
8 -alkylene, as in 1,4-butylenediamine, 1,5-pentylenediamine, 25 hexamethylenediamine, heptamethylenediamine, and octamethylenediamine. The diamine having two primary amino groups is especially hexamethylenediamine. A polyamine having at least three primary amino groups can moreover optionally be 30 used in the process of the invention (component iii.2). Said component (iii.2) comprises three or more primary amino groups and can moreover also comprise one or more secondary and/or tertiary amino groups. 35 Examples of these amines are 3-(2-aminoethyl)aminopropylamine, N,N-bis(3 aminopropyl)ethylenediamine, N,N-bis(3-aminopropyl)butanediamine,
N,N,N',N'
tetra(3-aminopropyl)ethylenediamine, N,N,N',N'-tetra(3-aminopropyl)butylenediamine, tris(aminoethyl)amine, tris(aminopropyl)amine, tris(aminohexyl)amine, trisaminohexane, 4-aminomethyl-1,8-octamethylenediamine, trisaminononane, or 40 amine-terminated polyoxyalkylene polyols of functionality three or higher (e.g. Jeffamines, for example polyetheramine T403 or polyetheramine T5000) with a molecular weight which is preferably from 300 to 10 000.
19 Among these, preference is given to tris(aminoethyl)amine, tris(aminopropyl)amine, and Jeffamines, for example polyetheramine T403 or polyetheramine T5000. 5 Said component (iii.2) is especially useful in the process of the invention when the intention is that the degree of branching set for the polymers is higher than possible with the di- or polyamine (iii. 1) alone, because polyamines having at least three primary amino groups provide access to further branching possibilities, alongside the melamine (ii) that must be used. The secondary and/or tertiary amino groups comprised in the 10 polyamine (iii.1) are less reactive than the primary amino groups and, under the reaction conditions of the process of the invention, mostly have only small capability, if any capability at all, for entering into a condensation reaction and therefore forming a branching site. In any instance they have in essence less capability than component (iii.2) for forming branching sites. 15 If, in contrast, the intention is to have a smaller degree of branching, it is clearly possible to use, in the process of the invention, at least one amine having a primary amino group (components iii.3). 20 This component is an amine having a single primary amino function and optionally having one or more secondary and/or tertiary amino groups. Examples of primary amines having no further secondary/tertiary amino functions (primary monoamines) are compounds of the formula R-NH 2 , in which R is an aliphatic, 25 alicyclic, aliphatic-alicyclic, aromatic, or araliphatic radical, which, of course, comprises no amino groups. Examples here are methylamine, ethylamine, propylamine, isopropylamine, n-butylamine, sec-butylamine, isobutylamine, tert-butylamine, pentylamine, 30 hexylamine, ethanolamine, propanolamine, isopropanolamine, pentanolamine, (2-methoxyethyl)amine, (2-ethoxyethyl)amine, (3-methoxypropyl)amine, (3-ethoxypropyl)amine, [3-(2-ethylhexyl)propyl]amine, 2-(2-eminoethoxy)ethanol, cyclohexylamine, aminomethylcyclohexane, aniline, benzylamine, and the like. 35 Examples of primary amines having one or more secondary and/or tertiary amino functions (polyamines having a (single) primary amino group) are N-methylethylene 1,2-diamine, N,N-dimethylethylene-1,2-diamine, N-ethylethylene-1,2-diamine, N,N-diethylethylene-1,2-diamine, N-methylpropylene-1,3-diamine, N,N-dimethylpropylene-1,3-diamine, N-ethylpropylene-1,3-diamine, 40 N,N-diethylpropylene-1,3-diamine, N-methylbutylene-1,4-diamine, N,N-dimethylbutylene-1,4-diamine, N-methylpentylene-1,5-diamine, N,N-dimethylpentylene-1,5-diamine, N-methylhexylene-1,6-diamine, 20 N, N-dimethylhexylene-1,6-diamine, N-methyldiethylenetriamine, N,N-dimethyldiethylenetriamine, N-methyltriethylenetetramine, N,N-dimethyltriethylenetetramine, N-methyltetraethylenepentamine, N,N-dimethyltetraethylenepentamine,
(
3 -(methylamino)propyl)(3-aminopropyl)amine, 5 (3-(dimethylamino)propyl)(3-aminopropyl)amine, (2-aminoethyl)ethanolamine, N-(2-hydroxyethyl)-1,3-propanediamine, N-methyldiaminocyclohexane, N,N-dimethyldiaminocyclohexane, N-methylphenylenediamine, and the like. It is preferable to use, as component (iii.3), primary monoamines, i.e. amines having a 10 single primary amino group, and having no further secondary or tertiary amino functions. In another embodiment of the invention, at least one melamine derivative (component iv) is used as further starting material in component B) of the invention. 15 It is preferable that the melamine derivative has been selected from benzoguanamine, substituted melamines, and melamine condensates. The melamine condensates have preferably been selected from melam, melem, melon, 20 and higher condensates. Melam (empirical formula C 6 -HgNii) is a dimeric condensate derived from 2,4-diamino-6-chloro-s-triazine with melamine. Melem (empirical formula
C
6
H
6
M
10 ) is tri-amino-substituted tri-s-triazine (1,3,4,6,7,9,9b-heptaazaphenalene). Melon (empirical formula C 6
H
3 Nq) is likewise a heptazine. 25 The molar ratio of component (i) to component (ii) is preferably from 50:1 to 1:50, particularly preferably from 10:1 to 1:10, more preferably from 8:1 to 1:8, still more preferably from 4:1 to 1:8, in particular from 2:1 to 1:5, and especially from 1:1 to 1:5. The molar ratio of component (i) to component (iii) is preferably from 10:1 to 1:50, 30 particularly preferably from 2:1 to 1:50, more preferably from 2:1 to 1:25, still more preferably from 1:1 to 1:20, in particular from 1:2.5 to 1:15, and especially from 1:5 to 1:15. It is particularly preferable to use components (i), (ii), and (iii) in molar ratios that 35 comply with the following relationship: The ratio of Amount of component (i) [mol] Amount of component (ii) [mo Amount of component (iii) [mol] 2 3 is preferably in the range from 0.05:1 to 0.75:1, particularly preferably from 0.075:1 to 40 0.5:1, and in particular from 0.1:1 to 0.4:1.
21 The molar ratio of components (i) and (ii) here is preferably in the ranges stated above. If component (iv) is used, it preferably replaces a portion of component (i). The amounts used of this material are preferably such as to replace from 1 to 75 mol% of 5 component (i), particularly preferably from 1 to 50 mol%, and in particular from 1 to 25 mol%. The reaction of components (i), (ii), (iii), and optionally (iv) preferably takes place in the presence of an acidic catalyst in the process of the invention. 10 Suitable acidic catalysts are either Bronsted acids or Lewis acids. Suitable Bronsted acids are either inorganic acids, such as mineral acids, e.g. hydrofluoric acid, hydrochloric acid, hydrobromic acid, nitric acid, sulfuric acid, 15 phosphoric acid, or amidosulfonic acid, or else ammonium salts, such as ammonium fluoride, ammonium chloride, ammonium bromide, or ammonium sulfate, or else organic acids, such as methanesulfonic acid, acetic acid, trifluoroacetic acid, and p-toluenesulfonic acid. 20 Other suitable Bronsted acids are the ammonium salts of organic amines, such as ethylamine, diethylamine, propylamine, dipropylamine, butylamine, dibutylamine, aniline, benzylamine, or melamine, and also the ammonium salts of urea. Suitable Lewis acids are all of the halides of metals or of semimetals, where the metal 25 or semimetal in the halide has an electron-pair vacancy. Examples of these are BF 3 , BCla, BBr 3 , AIF 3 , AICl 3 , AIBr 3 , ethylaluminum dichloride, diethylaluminum chloride, TiF 4 , TiC1 4 , TiBr 4 , VCis, FeF 3 , FeC1 3 , FeBr 3 , ZnF 2 , ZnC1 2 , ZnBr 2 , Cu(l)F, Cu(I)CI, Cu(I)Br, Cu(II)F 2 , Cu(II)C2, Cu(ll)Br 2 , Sb(ll)F 3 , Sb(V)F 5 , Sb(Ill)C1 3 , Sb(V)C1 5 , Nb(V)C1 5 , Sn(II)F 2 , Sn(II)C 2 , Sn(II)Br 2 , Sn(IV)F 4 , Sn(IV)Cl 4 , and Sn(IV)Br 4 . 30 However, it is preferable to use Bronsted acids. Among these, preference is given to the inorganic acids, and in particular to the ammonium salts, such as ammonium chloride or ammonium bromide. Ammonium chloride is especially used. 35 The reaction of the components preferably takes place at elevated temperature. The reaction temperature is preferably from 40 to 3000C, particularly preferably from 100 to 2500C, and in particular from 150 to 2300C. The reaction can be carried out either at atmospheric pressure or at elevated pressure, 40 e.g. at a pressure of from 1 to 20 bar or from 1 to 15 bar or from 10 to 15 bar. The pressure here is often generated exclusively via the ammonia liberated during the course of the reaction, during condensation of components (i), (ii), (iii), and optionally 22 (iv); the pressure therefore increases as the reaction proceeds and can then be adjusted to the desired value. However, if the intention is to carry out the reaction at elevated pressure, the pressure 5 can also be generated by way of an inert gas, e.g. via introduction of nitrogen, argon, or carbon dioxide, preferably of nitrogen. This is clearly useful in particular when the intention is to carry out the reaction at elevated pressure from the start, i.e. before any significant pressure can be produced via the ammonia formed. 10 The reaction pressure is in particular prescribed via the nature of the amines (component iii) used. By way of example, the reaction can be carried out at atmospheric pressure if the boiling point of the at least one amine used is above the reaction temperature. If, in contrast, the boiling point is below the reaction temperature, it is of course advantageous to carry out the reaction at elevated pressure. However, 15 even in the case of amines with boiling point above the reaction temperature, it can sometimes be advantageous to carry out the reaction at superatmospheric pressure, for example in order to achieve a higher reaction rate. The pressure can be adjusted as desired by using superfluous ammonia discharged from the reaction zone, for example via passage through a pressure-release valve which has been adjusted to the 20 appropriate value. If an inert gas is used to generate the pressure, the desired pressure is set by way of conventional control equipment, e.g. by way of pressure valves. If desired, the reaction can be carried out in a suitable solvent. Suitable solvents are inert, and this means that, under the prevailing reaction conditions, they do not react 25 with the starting materials, intermediates, or products, and that under the prevailing reaction conditions they are not themselves degraded, for example via thermal decomposition. Examples of suitable solvents are chlorinated aliphatic or aromatic hydrocarbons, e.g. methylene chloride, chloroform, dichloroethane, trichloroethane, chlorobenzene, chlorotoluene, and o-dichlorobenzene, and open-chain and cyclic 30 ethers, e.g. diethyl ether, dipropyl ether, tert-butyl methyl ether, tert-butyl ethyl ether, tetrahydrofuran, and 1,4-dioxane, polar aprotic solvents, e.g. N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and acetonitrile, and polar protic solvents, e.g. polyols or polyether polyols, e.g. ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, or polyethylene glycol. Preferred solvents are the 35 abovementioned polyols, or, respectively, polyether polyols. However, it is preferable that the reaction is carried out in bulk, i.e. without additional solvent. In this case, the amine (component iii) preferably serves as solvent, particularly if it is used in excess. 40 The reaction can be carried out by mixing all of the components and reacting them by heating to the desired reaction temperature. As an alternative, it is also possible to 23 begin by adding a portion of the components, and to introduce the remaining constituents gradually, the sequence of addition here being of relatively little importance. However, since melamine is generally the most sparingly soluble component, it has proven successful in practice to use the other components, i.e. 5 component (i), component (iii), optionally component (iv), and optionally the acidic catalyst and optionally the solvent, and possibly also a portion of the melamine, as initial charge, and to bring these to the desired reaction temperature, and gradually to introduce the remaining melamine, continuously or in portions. 10 In another method that has proved successful, particularly if component (i) is urea, some of this is not used as an initial charge but instead is gradually introduced, continuously or in portions. The method of addition of the individual reactants is advantageously such as to ensure 15 that they are completely dissolved, so as to maximize conversion in the condensation reaction. The reaction is generally carried out in reaction vessels conventional for such condensation reactions, for example in heatable stirred reactors, pressure vessels, or 20 stirred autoclaves. The reaction mixture is generally allowed to react until a desired maximum viscosity has been reached. The viscosity can be determined by taking the specimen and using conventional determination methods, for example with a viscometer; however, a sharp 25 increase in viscosity is often apparent visually during the course of the reaction, for example via foaming of the reaction mixture. The reaction is preferably terminated when the viscosity of the reaction mixture is at most 100 000 mPas, e.g. from 250 to 100 000 mPas, or from 500 to 100 000 mPas, or 30 from preferably 750 to 100 000 mPas (at 100*C), particularly preferably at most 50 000 mPas, e.g. from 250 to 50 000 mPas, or from 500 to 50 000 mPas, or from preferably 750 to 50 000 mPas (at 100*C), and in particular at most 10 000 mPas, e.g. from 250 to 10 000 mPas, or from 500 to 10 000 mPas, or from preferably 750 to 10 000 mPas (at 100*C). 35 When no further rise in the viscosity of the reaction mixture is intended, the reaction is terminated. The reaction is preferably terminated by lowering the temperature, preferably by 40 lowering the temperature to < 1000, e.g. from 20 to < 1000, preferably to < 50*C, e.g. to from 20 to < 50*C.
24 As a function of the intended application of the resultant polycondensate, it can be necessary or desirable to work up and purify the resultant reaction mixture. Conventional methods of work-up/purification can be used, an example being deactivation or removal of the catalyst, and/or removal of solvent and of unreacted 5 starting materials. To remove the acidic catalyst, the resultant reaction product can by way of example be treated with a base, e.g. with sodium hydroxide solution or potassium hydroxide solution. The salts that precipitate during this process are advantageously then 10 removed, for example via filtration. If the viscosity of the product is very high, for example more than 5000 mPas (at 25 0 C), this work-up can take place at an elevated temperature, for example at at least 50 0 C or at at least 75 0 C, or at at least 100*C. As an alternative, or in addition, the filtration process can take place under reduced pressure. 15 However, the purity level of the resultant polycondensates is adequate for numerous applications, and in these cases no further work-up or purification is therefore required and the product can be introduced directly into the further intended use thereof. 20 The polymers B) are highly branched polymers and in essence are not crosslinked polymers. Preferred components B) are polymers as described above which are subsequently modified. 25 The modification can take place by a method based on the process of EP 09179490.9 via at least one compound which, using amino groups, can enter into a condensation or addition reaction, preferably selected among aliphatic monocarboxylic acids or derivatives thereof, polycarboxylic acids or derivatives thereof, aliphatic, cycloaliphatic, 30 or aromatic optionally capped isocyanates, aliphatic monoamines, aliphatic polyamines, amine-terminated polyethers, alkylene oxides, aldehydes, ketones, and aldehydes in combination with a CH-acidic compound or with a hydroxyaromatic compound. 35 Aliphatic monocarboxylic acids are preferably those having from 1 to 22 carbon atoms, e.g. formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, nonadecanoic acid, tuberculostearic acid, 40 arachic acid, behenic acid, palmitoleic acid, oleic acid, erucic acid, sorbic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidonic acid, clupanodonic acid, and docosahexaenoic acid.
25 Suitable carboxylic acid derivatives are any of the derivatives suitable for reacting with the amino groups of the polymer from step (i) and, respectively, (ii) to give an amide bond. Among these are halides, in particular acyl chlorides, anhydrides, and esters. 5 The anhydrides can be either the symmetrical anhydrides or asymmetrical anhydrides. A selection of the latter is such that the "foreign" acid group can easily be displaced by the amino groups of the polymer from step (i) or (ii). Examples of suitable acid derivatives with which the abovementioned carboxylic acid can form suitable mixed 10 anhydrides are the esters of chloroformic acid, e.g. isopropyl chloroformate and isobutyl chloroformate, or of chloroacetic acid. Suitable esters are in particular the C-C 4 -alkyl esters, e.g. the methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, or tert-butyl esters. However, other suitable 15 esters are those that derive from C 2
-C
6 polyols, e.g. glycol, glycerol, trimethylolpropane, erythritol, pentaerythritol, and sorbitol, preference being given to the glycerol ester. If polyol esters are used, it is possible to use mixed esters, i.e. esters having different carboxylic acid radicals. Active esters are also suitable, these formally being obtained via reaction of the acid with an active-ester-forming alcohol, such as 20 p-nitrophenol, N-hydroxybenzotriazole (HOBt), N-hydroxysuccinimide, or OPfp (pentafluorophenol). It is preferable to use the carboxylic acids themselves (i.e. not derivatives thereof). 25 Examples of suitable polycarboxylic acids and derivatives thereof are ap-dicarboxylic acids or derivatives thereof, e.g. oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, sorbic acid, polyalkylene-substituted succinic acid, and derivatives thereof. Polyalkylene substituted succinic acid is preferably polyisobutylene-substituted succinic acid, 30 obtainable by way of example via reaction of polyisobutene with maleic anhydride under the reaction conditions of an ene reaction. The number-average molecular weight Ma of the polyalkenyl radicals, especially the polyisobutenyl radicals, is preferably from 100 to 5000, particularly preferably from 200 to 1000. Reference is made to the statements above in relation to suitable acid derivatives. In the case of the 35 dicarboxylic acid, preference is given to use of the anhydrides, preferably the internal anhydrides (i.e. succinic anhydride, maleic anhydride, adipic anhydride, etc.). Examples of suitable aliphatic, cycloaliphatic, or aromatic optionally capped isocyanates are methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, pentyl isocyanate, hexyl isocyanate, cyclohexyl isocyanate, phenyl 40 isocyanate, and the like. Suitable aliphatic monoamines are preferably primary or secondary, particularly 26 preferably primary. Examples of these are methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, [3-(2-ethylhexyl)propyl]amine, and the like. 5 Examples of suitable aliphatic polyamines are polyethyleneimines, polypropylene polyamines, polybutylene polyamines, polypentylene polyamines, and the like. Reference may be made to EP 09179490.0 for other suitable modifiers. 10 The molding compositions of the invention can comprise, as component C), up to 70% by weight, preferably up to 50% by weight, of further additives. Fibrous or particulate fillers Cl) that may be mentioned are carbon fibers, glass fibers, glass beads, amorphous silica, calcium silicate, calcium metasilicate, magnesium 15 carbonate, kaolin, chalk, powdered quartz, mica, barium sulfate, and feldspar, and the amounts of these that can be used are from I to 50% by weight, in particular from 5 to 45% by weight, preferably from 10 to 40% by weight. Preferred fibrous fillers that may be mentioned are carbon fibers, aramid fibers, and 20 potassium titanate fibers, particular preference being given to glass fibers in the form of E glass. These can 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 25 improve compatibility with the thermoplastic. Suitable silane compounds have the general formula:
(X-(CH
2 )n)k-Si-(O-CmH 2 m+1)4-k 30 where the definitions of the substituents are as follows: X NH2-, CH -CH-, HO-, 35 n is a whole number from 2 to 10, preferably 3 to 4, m is a whole number from 1 to 5, preferably 1 to 2, and k is a whole number from I to 3, preferably 1. Preferred silane compounds are aminopropyltrimethoxysilane, 40 aminobutyltrimethoxysilane, aminopropyltriethoxysilane and aminobutyltriethoxysilane, and also the corresponding silanes which comprise a glycidyl group as substituent X.
27 The amounts of the silane compounds generally used for surface-coating are from 0.01 to 2% by weight, preferably from 0.025 to 1.0% by weight and in particular from 0.05 to 0.5% by weight (based on E)). 5 Acicular mineral fillers are also suitable. For the purposes of the invention, acicular mineral fillers are mineral fillers with strongly developed acicular character. An example is acicular wollastonite. The mineral 10 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 optionally have been pretreated with the abovementioned silane compounds, but the pretreatment is not essential. Other fillers which may be mentioned are kaolin, calcined kaolin, wollastonite, talc and 15 chalk, and also lamellar or acicular nanofillers, the amounts of these preferably being from 0.1 to 10%. Materials preferred for this purpose are boehmite, bentonite, montmorillonite, vermiculite, hectorite, and laponite. The 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 20 nanocomposites gives a further increase in mechanical strength. The molding compositions of the invention can comprise, as component C2), 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. 25 Preference is given to the salts of Al, of alkali metals, or of alkaline earth metals, or esters or amides of fatty acids having from 10 to 44 carbon atoms, preferably having from 12 to 44 carbon atoms. 30 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. 35 It is also possible to use a mixture of various salts, in any desired mixing ratio. 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 40 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 28 n-butanol, 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, 5 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. 10 It is also possible to use a mixture of various esters or amides, or of esters with amides in combination, in any desired mixing ratio. The molding compositions of the invention can comprise, as component C3), from 0.05 15 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 copper stabilizer, preferably of a Cu(I) halide, in particular in a mixture with an alkali metal halide, preferably KI, in particular in the ratio 1:4, or of a sterically hindered phenol, or a mixture of these. 20 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 25 molecular distribution in the polyamide. This is achieved if a concentrate comprising the 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. By way of example, 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 30 iodide or copper bromide and potassium iodide. The copper concentration in the solid homogeneous 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. 35 Suitable polyamides for the concentrate are homopolyamides and copolyamides, in particular nylon-6 and nylon-6,6. Suitable sterically hindered phenols D3) are in principle all of the compounds which have a phenolic structure and which have at least one bulky group on the phenolic ring. 40 It is preferable to use, for example, compounds of the formula 29 R2 R3 HO RR where:
R
1 and R 2 are an alkyl group, a substituted alkyl group, or a substituted triazole group, 5 and where the radicals R 1 and R 2 may 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 abovementioned type are described by way of example in DE A 27 02 661 (US-A 4 360 617). 10 Another group of preferred sterically hindered phenols is provided by those derived from substituted benzenecarboxylic acids, in particular from substituted benzenepropionic acids. 15 Particularly preferred compounds from this class are compounds of the formula R6 R HO CH 2
--CH
2
--C-O-R--C-H---CH
2 \/ OH where R 4 , R 5 , R 7 , and R 8 , independently of one another, are C 1
-C
8 -alkyl groups which 20 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-0 bonds. Preferred compounds corresponding to these formulae are 25 CH CH3 CH CH3 CH 0 0 HO C/--CH- 2 - -- O-CH--CH - OCH-CH-CH 2 -CH-O-CH-CH2 /OH
CH
3
CH
3 (Irganox@ 245 from BASF SE) 30 CH3 CH3 CH CH CH/ 0 0 o II
II-H
3 HO / CH 2
-CH
2
-O(CH
2 )s-O-CHi-CH 2 OH CH3 CH 3 CH CH 3 (Irganox@ 259 from BASF SE) 5 All of the following should be mentioned as examples of sterically hindered phenols: 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 1,6-hexanediol bis[3-(3,5-di-tert-butyl 4-hydroxyphenyl)propionate], pentaerythrityl tetrakis[3-(3,5-di-tert-butyl 4-hydroxyphenyl)propionate], distearyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 10 2,6,7-trioxa-1-phosphabicyclo[2.2.2]oct-4-ylmethyl 3,5-di-tert-butyl 4-hydroxyhydrocinnamate, 3,5-di-tert-butyl-4-hydroxyphenyl 3,5-distearylthiotriazylamine, 2-(2'-hydroxy-3'-hydroxy-3',5'-di-tert-butylphenyl) 5-chlorobenzotriazole, 2,6-di-tert-butyl-4-hydroxymethylphenol, 1,3,5-trimethyl 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 4,4'-methylenebis(2,6-di-tert 15 butylphenol), 3,5-di-tert-butyl-4-hydroxybenzyldimethylamine. Compounds which have proven particularly effective and which are therefore used with preference are 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 1,6-hexanediol bis(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (Irganox@ 259), pentaerythrityl 20 tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and also N,N' hexamethylenebis-3,5-di-tert-butyl-4-hydroxyhydrocinnamide (Irganox® 1098), and the product Irganox@ 245 described above from BASF SE, which has particularly good suitability. 25 The amount comprised of the antioxidants C), which can be used individually or as a mixture, is from 0.05 up to 3% by weight, preferably from 0.1 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 C). 30 In some instances, sterically hindered phenols having not 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 prolonged periods. 35 The molding compositions of the invention can comprise, as component C4), from 0.05 to 5% by weight, preferably from 0.1 to 2% by weight, and in particular from 0.25 to 31 1.5% by weight, of a nigrosine. Nigrosines are generally a group of black or gray phenazine dyes (azine dyes) related to the indulines and taking various forms (water-soluble, oleosoluble, spirit-soluble), 5 used in wool dyeing and wool printing, in black dyeing of silks, and in the coloring of leather, of shoe creams, of varnishes, of plastics, of stoving lacquers, of inks, and the like, and also as microscopy dyes. Nigrosines are obtained industrially via heating of nitrobenzene, aniline, and aniline 10 hydrochloride with metallic iron and FeC1 3 (the name being derived from the Latin niger = black). Component C4) can be used in the form of free base or else in the form of salt (e.g. hydrochloride). 15 Further details concerning nigrosines can be found by way of example in the electronic encyclopedia R6mpp Online, Version 2.8, Thieme-Verlag Stuttgart, 2006, keyword "Nigrosine". 20 The molding compositions of the invention can comprise, as component C5), 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 with a particle size of at most 10 pm (d 50 value), where the powder is preferably obtainable via thermal decomposition of pentacarbonyliron. 25 Iron occurs in a number of allotropes: 1. a-Fe (ferrite) forms space-centered cubic lattices, is magnetizable, dissolves a small amount of carbon, and occurs in pure iron up to 928 0 C. At 7700C (Curie 30 temperature) it loses its ferromagnetic properties and becomes paramagnetic; iron in the temperature range from 770 to 9280C is also termed [-Fe. At normal temperature and at a pressure of at least 13 000 MPa, a-Fe becomes what is known as E-Fe with a reduction of about 0.20 cm 3 /mol in volume, whereupon density increases from 7.85 to 9.1 (at 20 000 MPa). 35 2. y-Fe (austenite) forms face-centered cubic lattices, is nonmagnetic, dissolves a large amount of carbon, and is observable only in the temperature range from 928 to 13980C. 40 3. b-Fe, space-centered, exists at from 13980C to the melting point of 15390C. Metallic iron is generally silver-white, density 7.874 (heavy metal), m.p. 15390C, boiling 32 point 2880*C; specific heat (from 18 to 100*C) about 0.5 g- K- 1 , tensile strength from 220 to 280 N/mm 2 . The values apply to chemically pure iron. Industrial production of iron uses smelting of iron ores, iron slags, calcined pyrites, or 5 blast-furnace dust, and resmelting of scrap and alloys. The iron powder of the invention is produced via thermal decomposition of pentacarbonyliron, preferably at temperatures of from 150*C to 350*C. The particles thus obtainable have a preferably spherical shape, therefore being spherical or almost 10 spherical (another term used being spherolitic). Preferred iron powder has the particle size distribution described below; particle size distribution here is determined by means of laser scattering in very dilute aqueous suspension (e.g. using a Beckmann LS13320). The particle size (and distribution) 15 described hereinafter can optionally be obtained via grinding and/or sieving. da, here means that XX% of the total volume of the particles is smaller than the stated value. 20 d 50 values: at most 10 pm, preferably from 1.6 to 8 pm, in particular from 2.9 to 7.5 pm, very particularly from 3.4 to 5.2 pm d 1 0 values: preferably from 1 to 5 pm, in particular from 1 to 3 pm, and very particularly from 1.4 to 2.7 pm 25 d 9 o values: preferably from 3 to 35 pm, in particular from 3 to 12 pm, and very particularly from 6.4 to 9.2 pm. Component B) preferably has iron content of from 97 to 99.8 g/100 g, preferably from 30 97.5 to 99.6 g/1 00 g. 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 via 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, 35 and in particular from 0.4 to 1.1 g/100 g. This C content in the preferred iron powders corresponds to that of powders which are not reduced using hydrogen after the thermal decomposition process. The carbon content is usually determined by combustion of the sample in a stream of 40 oxygen and then using IR to detect the resultant C02 gas (by means of a Leco CS230 or CS-mat 6250 from Juwe) by a method based on ASTM El 019.
33 Nitrogen content is preferably at most 1.5 g/1 00 g, preferably from 0.01 to 1.2 g/1 00 g. Oxygen content is preferably at most 1.3 g/1 00 g, preferably from 0.3 to 0.65 g/1 00 g. N and 0 are determined via heating of the specimen to about 21000C in a graphite furnace. The oxygen obtained from the specimen here is converted to CO and 5 measured by way of an IR detector. The N liberated under the reaction conditions from the N-containing compounds is discharged with the carrier gas and detected and recorded by means of TCD (Thermal Conductivity Detector) (both methods based on ASTM E1019). 10 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 when the powder is, for example, charged to the container and compacted by vibration. Iron powders to which further preference is given can have been surface-coated with iron phosphate, with iron phosphite, or with SiO 2 . 15 BET surface area to DIN ISO 9277 is preferably from 0.1 to 10 m 2 /g, in particular from 0.1 to 5 m 2 /g, and preferably from 0.2 to 1 m 2 /g, and in particular from 0.4 10 1 m 2 /g. In order to achieve particularly good dispersion of the iron particles, a masterbatch may be used, involving a polymer. Suitable polymers for this purpose are polyolefins, 20 polyesters, or polyamides, and it is preferable here that the masterbatch polymer is the same as component A). The mass fraction of the iron in the polymer is generally from 15 to 80% by mass, preferably from 20 to 40% by mass. Examples of other conventional additives C) are amounts of up to 25% by weight, 25 preferably up to 20% by weight, of elastomeric polymers (also often termed impact modifiers, elastomers, or rubbers). These are very generally copolymers preferably composed of at least two of the following monomers: ethylene, propylene, butadiene, isobutene, isoprene, chloroprene, 30 vinyl acetate, styrene, acrylonitrile and acrylates and/or methacrylates having from 1 to 18 carbon atoms in the alcohol component. Polymers of this type are described, for example, in Houben-Weyl, Methoden der organischen Chemie, Vol. 14/1 (Georg-Thieme-Verlag, Stuttgart, Germany, 1961), 35 pages 392-406, and in the monograph by C.B. Bucknall, "Toughened Plastics" (Applied Science Publishers, London, UK, 1977). Some preferred types of such elastomers are described below. 40 Preferred types of such elastomers are those known as ethylene-propylene (EPM) and ethylene-propylene-diene (EPDM) rubbers.
34 EPM rubbers generally have practically no residual double bonds, whereas EPDM rubbers may have from 1 to 20 double bonds per 100 carbon atoms. Examples which may be mentioned of diene monomers for EPDM rubbers are 5 conjugated dienes, such as isoprene and butadiene, non-conjugated dienes having from 5 to 25 carbon atoms, such as 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 2,5-dimethyl-1,5-hexadiene and 1,4-octadiene, cyclic dienes, such as cyclopentadiene, cyclohexadienes, cyclooctadienes and dicyclopentadiene, and also alkenylnorbornenes, such as 5-ethylidene-2-norbornene, 5-butylidene-2-norbornene, 10 2-methallyl-5-norbornene and 2-isopropenyl-5-norbornene, and tricyclodienes, such as 3-methyltricyclo[5.2.1.0 2 .]-3,8-decadiene, and mixtures of these. Preference is given to 1,5-hexadiene, 5-ethylidenenorbornene and dicyclopentadiene. The diene content of the EPDM rubbers is preferably from 0.5 to 50% by weight, in particular from 1 to 8% by weight, based on the total weight of the rubber. 15 EPM rubbers and EPDM rubbers may preferably also have been grafted with reactive carboxylic acids or with derivatives of these. Examples of these are acrylic acid, methacrylic acid and derivatives thereof, e.g. glycidyl (meth)acrylate, and also maleic anhydride. 20 Copolymers of ethylene with acrylic acid and/or methacrylic acid and/or with the esters of these acids are another group of preferred rubbers. The rubbers may also comprise dicarboxylic acids, such as maleic acid and fumaric acid, or derivatives of these acids, e.g. esters and anhydrides, and/or monomers comprising epoxy groups. These 25 dicarboxylic acid derivatives or monomers comprising epoxy groups are preferably incorporated into the rubber by adding to the monomer mixture monomers comprising dicarboxylic acid groups and/or epoxy groups and having the general formulae I or 11 or Ill or IV 30 R 1
C(COOR
2 )=C(COOR3)R4 (1) R R 4 C C O O O 00 CI 35 0
CHR
7 =CH- (CH 2 )m - O - (CHR),--CH - CHR 5 (III) CH-- CR9-COO- (-CH 2)p-CH-CHR (IV) 0 where R 1 to R 9 are hydrogen or alkyl groups having from 1 to 6 carbon atoms, and m is a whole number from 0 to 20, g is a whole number from 0 to 10 and p is a whole 5 number from 0 to 5. The radicals R 1 to R 9 are preferably hydrogen, where m is 0 or 1 and g is 1. The corresponding compounds are maleic acid, fumaric acid, maleic anhydride, allyl glycidyl ether and vinyl glycidyl ether. 10 Preferred compounds of the formulae 1, 11 and IV are maleic acid, maleic anhydride and (meth)acrylates comprising epoxy groups, such as glycidyl acrylate and glycidyl methacrylate, and the esters with tertiary alcohols, such as tert-butyl acrylate. Although the latter have no free carboxy groups, their behavior approximates to that of the free 15 acids and they are therefore termed monomers with latent carboxy groups. The copolymers are advantageously composed of from 50 to 98% by weight of ethylene, from 0.1 to 20% by weight of monomers comprising epoxy groups and/or methacrylic acid and/or monomers comprising anhydride groups, the remaining amount 20 being (meth)acrylates. Particular preference is given to copolymers composed of from 50 to 98% by weight, in particular from 55 to 95% by weight, of ethylene, 25 from 0.1 to 40% by weight, in particular from 0.3 to 20% by weight, of glycidyl acrylate and/or glycidyl methacrylate, (meth)acrylic acid and/or maleic anhydride, and from 1 to 45% by weight, in particular from 5 to 40% by weight, of n-butyl acrylate 30 and/or 2-ethylhexyl acrylate. Other preferred (meth)acrylates are the methyl, ethyl, propyl, isobutyl and tert-butyl esters. 35 Comonomers which may be used alongside these are vinyl esters and vinyl ethers.
36 The ethylene copolymers described above may be prepared by processes known per se, preferably by random copolymerization at high pressure and-elevated temperature. Appropriate processes are well-known. 5 Other preferred elastomers are emulsion polymers whose preparation is described, for example, by Blackley in the monograph "Emulsion Polymerization". The emulsifiers and catalysts which can be used are known per se. In principle it is possible to use homogeneously structured elastomers or else those 10 with a shell structure. The shell-type structure is determined by the sequence of addition of the individual monomers. The morphology of the polymers is also affected by this sequence of addition. Monomers which may be mentioned here, merely as examples, for the preparation of 15 the rubber fraction of the elastomers are acrylates, such as, for example, n-butyl acrylate and 2-ethylhexyl acrylate, corresponding methacrylates, butadiene and isoprene, and also mixtures of these. These monomers may be copolymerized with other monomers, such as, for example, styrene, acrylonitrile, vinyl ethers and with other acrylates or methacrylates, such as methyl methacrylate, methyl acrylate, ethyl 20 acrylate or propyl acrylate. The soft or rubber phase (with a glass transition temperature of below 0*C) of the elastomers may be the core, the outer envelope or an intermediate shell (in the case of elastomers whose structure has more than two shells). Elastomers having more than 25 one shell may also have more than one shell composed of a rubber phase. If one or more hard components (with glass transition temperatures above 20*C) are involved, besides the rubber phase, in the structure of the elastomer, these are generally prepared by polymerizing, as principal monomers, styrene, acrylonitrile, 30 methacrylonitrile, a-methylstyrene, p-methylstyrene, or acrylates or methacrylates, such as methyl acrylate, ethyl acrylate or methyl methacrylate. Besides these, it is also possible to use relatively small proportions of other comonomers. It has proven advantageous in some cases to use emulsion polymers which have 35 reactive groups at their surfaces. Examples of groups of this type are epoxy, carboxy, latent carboxy, amino and amide groups, and also functional groups which may be introduced by concomitant use of monomers of the general formula Rio Ril 10 111
CH
2 =C--X-N-C--R 0 37 where the substituents can be defined as follows:
R
10 is hydrogen or a C-C 4 -alkyl group, 5 R' is hydrogen, a C-Cs-alkyl group or an aryl group, in particular phenyl,
R
12 is hydrogen, a Cl-C 1 o-alkyl group, a C6-C12-aryl group, or -OR 13 , 10 R 13 is a C-C 8 -alkyl group or a C6-C12-aryl group, which can optionally have substitution by groups that comprise 0 or by groups that comprise N, X is a chemical bond, a C-C 10 -alkylene group, or a C6-C12-arylene group, or 0 -C - Y 15 Y is O-Z or NH-Z, and Z is a C-C 1 o-alkylene or C6-C12-arylene group. 20 The graft monomers described in EP-A 208 187 are also suitable for introducing reactive groups at the surface. Other examples which may be mentioned are acrylamide, methacrylamide and substituted acrylates or methacrylates, such as (N-tert-butylamino)ethyl methacrylate, 25 (N,N-dimethylamino)ethyl acrylate, (N,N-dimethylamino)methyl acrylate and (N,N-diethylamino)ethyl acrylate. The particles of the rubber phase may also have been crosslinked. Examples of crosslinking monomers are 1,3-butadiene, divinylbenzene, diallyl phthalate and 30 dihydrodicyclopentadienyl acrylate, and also the compounds described in EP-A 50 265. It is also possible to use the monomers known as graft-linking monomers, i.e. monomers having two or more polymerizable double bonds which react at different rates during the polymerization. Preference is given to the use of compounds of this 35 type in which at least one reactive group polymerizes at about the same rate as the other monomers, while the other reactive group (or reactive groups), for example, polymerize(s) significantly more slowly. The different polymerization rates give rise to a certain proportion of unsaturated double bonds in the rubber. If another phase is then grafted onto a rubber of this type, at least some of the double bonds present in the 40 rubber react with the graft monomers to form chemical bonds, i.e. the phase grafted on has at least some degree of chemical bonding to the graft base.
38 Examples of graft-linking monomers of this type are monomers comprising allyl groups, in particular allyl esters of ethylenically unsaturated carboxylic acids, for example allyl acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate and diallyl itaconate, and 5 the corresponding monoallyl compounds of these dicarboxylic acids. Besides these there is a wide variety of other suitable graft-linking monomers. For further details reference may be made here, for example, to US patent 4 148 846. The proportion of these crosslinking monomers in the impact-modifying polymer is 10 generally up to 5% by weight, preferably not more than 3% by weight, based on the impact-modifying polymer. Some preferred emulsion polymers are listed below. Mention may first be made here of graft polymers with a core and with at least one outer shell, and having the following 15 structure: Type Monomers for the core Monomers for the envelope I 1,3-butadiene, isoprene, n-butyl styrene, acrylonitrile, methyl acrylate, ethylhexyl acrylate, or a methacrylate mixture of these I as I, but with concomitant use of as I crosslinking agents III as I or || n-butyl acrylate, ethyl acrylate, methyl acrylate, 1,3-butadiene, isoprene, ethylhexyl acrylate IV as I or 11 as I or 111, but with concomitant use of monomers having reactive I groups, as described herein V styrene, acrylonitrile, methyl first envelope composed of methacrylate, or a mixture of these monomers as described under I and |1 for the core, second envelope as described under I or IV for the envelope Instead of graft polymers whose structure has more than one shell, it is also possible to use homogeneous, i.e. single-shell, elastomers composed of 1,3-butadiene, isoprene 20 and n-butyl acrylate or of copolymers of these. These products, too, may be prepared by concomitant use of crosslinking monomers or of monomers having reactive groups. Examples of preferred emulsion polymers are n-butyl acrylate-(meth)acrylic acid copolymers, n-butyl acrylate/glycidyl acrylate or n-butyl acrylate/glycidyl methacrylate 25 copolymers, graft polymers with an inner core composed of n-butyl acrylate or based on butadiene and with an outer envelope composed of the abovementioned copolymers, and copolymers of ethylene with comonomers which supply reactive groups.
39 The elastomers described may also be prepared by other conventional processes, e.g. by suspension polymerization. Preference is also given to silicone rubbers, as described in DE-A 37 25 576, 5 EP-A 235 690, DE-A 38 00 603 and EP-A 319 290. It is, of course, also possible to use mixtures of the types of rubber listed above. The thermoplastic molding compositions of the invention can comprise, as component 10 C), 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. 15 Examples of oxidation retarders and heat stabilizers are sterically hindered phenols and/or phosphites and amines (e.g. TAD), hydroquinones, aromatic secondary amines, such as diphenylamines, various substituted members of these groups, and mixtures of these, in concentrations of up to 1 % by weight, based on the weight of the thermoplastic molding compositions. 20 UV stabilizers that may be mentioned, the amounts of which used are generally up to 2% by weight, based on the molding composition, are various substituted resorcinols, salicylates, benzotriazoles, and benzophenones. 25 Materials that can be added as colorants 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. 30 Materials that can be used as nucleating agents are sodium phenylphosphinate, aluminum oxide, silicon dioxide, and also preferably talc. The thermoplastic molding compositions of the invention can be produced by processes known per se, by mixing the starting components in conventional mixing 35 apparatus, such as screw-based extruders, Brabender mixers, or Banbury mixers, and then extruding the same. After extrusion, the extrudate can be cooled and pelletized. It is also possible to premix individual components and then to add the remaining starting materials individually and/or likewise in the form of a mixture. The mixing temperatures are generally from 230 to 320'C. 40 In another preferred mode of operation, components B) and C) can also optionally be mixed with a prepolymer, compounded, and pelletized. The pellets obtained are then 40 solid-phase condensed under an inert gas continuously or batchwise at a temperature below the melting point of component A) until the desired viscosity has been reached. The thermoplastic molding compositions of the invention feature good processability 5 together with good mechanical properties, and also markedly improved weld line strength and surface, and also thermal stability. These materials are suitable for the production of fibers, foils, and moldings of any type. Some examples follow: cylinder head covers, motorcycle covers, intake 10 manifolds, charge-air-cooler caps, plug connectors, gearwheels, cooling-fan wheels, and cooling-water tanks. In the electrical and electronic sector, improved-flow polyamides can be used to produce plugs, plug parts, plug connectors, membrane switches, printed circuit board 15 modules, microelectronic components, coils, 1/0 plug connectors, plugs for printed circuit boards (PCBs), plugs for flexible printed circuits (FPCs), plugs for flexible integrated circuits (FFCs), high-speed plug connections, terminal strips, connector plugs, device connectors, cable-harness components, circuit mounts, circuit-mount components, three-dimensionally injection-molded circuit mounts, electrical connection 20 elements, and mechatronic components. Possible uses in automobile interiors are for dashboards, steering-column switches, seat components, headrests, center consoles, gearbox components, and door modules, and possible uses in automobile exteriors are for door handles, exterior 25 mirror components, windshield-wiper components, windshield-wiper protective housings, grilles, roof rails, sunroof frames, engine covers, cylinder-head covers, intake pipes (in particular intake manifolds), windshield wipers, and also external bodywork components. 30 Possible uses of improved-flow polyamides in the kitchen and household sector are for the production of components for kitchen devices, e.g. fryers, smoothing irons, knobs, and also applications in the garden and leisure sector, e.g. components for irrigation systems, or garden devices, and door handles. 35 Examples 1. Use of various melamine polymers in polyamide The following components were used: 40 Component A Nylon-66 with intrinsic viscosity IV of 148 ml/g, measured on a 0.5% strength by weight solution in 96% strength by weight sulfuric acid at 25*C to ISO 307. (Ultramid@ A27 41 from BASF SE was used.) Components B Amine number was determined to DIN 53176. Viscosity was determined with a 5 rheometer (Physica MCR51 from Anton Paar GmbH, Graz, Austria). To determine solubility the product and the solvent were mixed in a ratio by weight of 10:90 and heated with a heat gun. The product is regarded as soluble if it does not precipitate on cooling. 10 B/1 Production of a highly branched melamine-tetraethylenepentamine polymer 1855 g : 9.8 mol of tetraethylenepentamine were used as initial charge, and 121.9 g a 2.28 mol of ammonium chloride were admixed as catalyst, and nitrogen at a low flow rate was applied. 441 g a 3.5 mol of melamine were added in 4 portions. After each 15 melamine addition here, the reaction mixture was heated to 200 0 C and stirred until the melamine had dissolved. After dissolution, the mixture was first cooled to 100*C before the next portion was added. After addition of the final portion, the reaction mixture was stirred at 200*C until no further viscosity rise (about 20 000 mPas at 75*C) occurred. After cooling, the catalyst was neutralized with 50% strength sodium hydroxide 20 solution, and sodium hydroxide formed here was removed by filtration by way of a pressure filter funnel at 900C. A yellow polymer was obtained, with the following properties: Viscosity (750C) 1 = 3800 mPas 25 Solubility: HFIP (= hexafluoroisopropanol), water Amine number: 677.7 mg KOH/g GPC: Mw = 13400 g/mol Mn = 5100 g/mol 30 B/2 Production of a functionalized, highly branched melamine polymer 2.8 mol of pentaethylenehexamine were used as initial charge, and 0.65 mol of ammonium chloride were admixed as catalyst, and nitrogen at a low flow rate was applied. 1 mol of melamine was added in 4 portions of 0.25 mol. After each melamine 35 addition here, the reaction mixture was heated to 2000C and stirred until the melamine had dissolved. After dissolution, the mixture was first cooled to 100*C before the next portion was added. After addition of the final portion, the reaction mixture was stirred at 2000C until no further viscosity rise (about 20 000 mPas at 750C) occurred. After cooling, the catalyst was neutralized with 50% strength sodium hydroxide solution, and 40 sodium hydroxide formed here was removed by filtration by way of a pressure filter funnel at 900C. A yellow polymer was obtained, with the following properties: 42 Viscosity (75 0 C) rj = 3250 mPas GPC (HFIP) M, = 6300, Mw = 24 400 Solubility: HFIP (= hexafluoroisopropanol), water Amine number: 665 mg KOH/g 5 The resultant polymer was used as initial charge in a flask and 0.2 mol of oleic acid were admixed. The mixture was heated to 120 and the resultant water of reaction was removed by distillation. The temperature was increased stepwise here to 1800C. Once no further water was formed, stirring was continued for a further hour at 1800C. This 10 gave a dark yellow polymer that flowed like honey and had the following properties: Viscosity (750C) 11 = 1500 mPas Solubility: HFIP (= hexafluoroisopropanol), water 15 Prior to compounding, components B/1 and B/2 were dried for 24 hours at 800C in vacuo. Component C/1 Glass fibers 20 Component C/2 Calcium stearate Component C/3 25 Cul/KI in a ratio of 1 : 4 (masterbatch of strength 20% in PA6) Component C/4 40% strength PA6 masterbatch with nigrosin 30 The molding compositions were produced in an ZSK 30 at throughput 25 kg/h and with a flat temperature profile at about 2600C. The following tests were carried out: Tensile test to ISO 527, mechanical properties prior to and after heat-aging at 200 and, 35 respectively, 220'C in a convection oven IV: c = 5 g/I in 96% strength sulfuric acid, ISO 307 Injection pressure was determined as pressure at the changeover point during injection molding of tensile specimens to ISO 527. 40 The tables give the constitutions of the molding compositions and the results of the tests.
43 Constitutions: Ex. A C/1 C/2 C/3 C/4 B1 B2 Injection IV (%) (%) (%) (%) (%) (%) (%) pressure (bar) (ml/g) 1 comp 67.45 30 0.35 0.3 1.9 0 0 327 153 1 66.95 30 0.35 0.3 1.9 0.5 0 249 148 2 66.95 30 0.35 0.3 1.9 0 0.5 259 140 Mechanical properties after heat-aging at 2200C 5 Example Modulus of elasticity [MPa] Oh 250h 500h 750h 1 comp 9830 10580 10200 8400 1 9950 10500 10430 10150 2 9890 10660 10440 9930 Example (Tensile stress at break) [MPa] Oh 250h 500h 750h I comp 187 158 121 71 1 192 182 154 128 2 191 177 147 113 Example (Tensile strain at break) [%] Oh 250h 500h 750h 1 comp 3.4 1.8 1.4 1.0 1 3.0 2.3 1.8 1.5 2 2.9 2.2 1.7 1.4 Mechanical properties after heat-aging at 2000C Example Modulus of elasticity [MPa] Oh 250h 500h 750h 1000h 1 comp 9830 10310 10420 10330 10320 1 9950 10520 10460 10230 10200 Example (Tensile stress at break) [MPa] Oh 250h 500h 750h .1000h 1 comp 187 172 146 141 129 1 192 185 166 160 140 10 Example (Tensile strain at break) [%] 44 Oh 250h 500h 750h 1000h 1 comp 3.4 2.2 1.7 1.6 1.5 1 3.0 2.3 1.9 1.9 1.6 11. Combination of melamine polymers with iron powder Components A/1, A/4, B1, and C1 to C4 are the same as in I. 5 Component C5 used was: Iron powder with CAS no. 7439-89-6. For determination of Fe, C, N, and 0 content, see pages 32-34 of the description. Fe g/100 g min. 97.7 IR detection C g/100 g max. 1.0 IRS N g/100 g max. 1.0 TCD o g/100 g max. 0.6 IRS 10 Particle size distribution: (laser scattering using Beckmann LS13320) d 10 from 1.4 to 2.7 mn d 50 from 2.9 to 4.2 pn d 9 o from 6.4 to 9.2 pm 15 BET surface area 0.44 m 2 /g (DIN ISO 9277) The production process and the test methods were the same as in 1. The constitution of the molding compositions was: 20 54.75 % by weight of A/1 10 % by weight of A/4 0.5 % by weight of B/1 30 % by weight of C/1 25 0.35 % by weight of C/2 1.5 % by weight of C/3 1.9 % by weight of C/4 1 % by weight of C/5 30 Mechanical properties after heat-aging at 200*C Ex. Modulus of elasticity (MPa) Oh 500 h 1000 h 1500 h 2000 h 2500 h 3000 h 1 9600 10100 10320 10100 10500 10100 9400 45 Ex. Tensile stress at break [MPa] Oh 500h 1000h 1500h 2000h 2500h 3000h 1 181 185 173 167 154 141 122 Ex. Tensile strain at break [%} 0 h 500 h 1000 h 1500 h 2000 h 2500 h 3000 h 1 3.3 2.7 2.4 2.4 2.1 1.8 1.6 Mechanical properties after heat-aging at 220"C Ex. Modulus of elasticity (MPa) 0 h 500 h 1000 h 1500 h 2000 h 2500 h 3000 h 1 9600 10350 10200 10400 10500 10400 10600 Bsp. Tensile stress at break [MPa] 0 h 500 h 1000 h 1500 h 2000 h 2500 h 3000 h 1 181 151 160 165 175 177 175 Ex. Tensile strain at break [%] Oh 500 h 1000 h 1500 h 2000 h 2500 h 3000 h 1 3.3 1.8 2.0 2.6 2.8 2.7 2.8 Comprises/comprising and grammatical variations thereof when used in this specification are to be taken to specify the presence of stated features, integers, steps or components or groups thereof, but do not preclude the presence or addition of one or more other features, integers, steps, components or groups thereof.

Claims (9)

1. A thermoplastic molding composition, comprising A) from 10 to 98% by weight of a thermoplastic polyamide, B) from 0.01 to 20% by weight of a highly branched melamine polymer or melamine-urea polymer, or a mixture of these, C) from 0 to 70% by weight of further additives, C3) from 0.05 to 3% by weight of a copper-containing stabilizer, where the total of the percentages by weight of components A) to C) is 100%.
2. The thermoplastic molding composition according to claim 1, comprising from 1 to 50% by weight of a fibrous or particulate additive C1.
3. The thermoplastic molding composition according to claim 1 or 2, in which the degree of branching of component B) is from 10 to 99.9%.
4. The thermoplastic molding composition according to any one of claims 1 to 3, in which the amine number (DIN 53176) of component B) is from 100 to 900 mg KOH/g.
5. The thermoplastic molding composition according to any one of claims 1 to 4, in which the number-average molar mass Mn of component B) is from 1000 to 40 000 g/mol (GPC).
6. The thermoplastic molding composition according to any one of claims 1 to 5, in which the weight-average molar mass Mw of component B) is from 1500 to 150 000 g/mol.
7. The thermoplastic molding composition according to any one of claims 1 to 6, comprising from 0.001 to 20% by weight of iron powder with a particle size of at most 10 pm (d 50 value) (component C5).
8. The use of the thermoplastic molding compositions according to any one of claims 1 to 7 for producing fibers, foils, and moldings of any type.
9. A fiber, foil, or molding, obtainable from the thermoplastic molding compositions according to any one of claims 1 to 8.
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