# Patent

## Title
Polyamide resistant to heat aging

## Abstract

Thermoplastic molding compositions, comprising

    A) from 10 to 99.999% by weight of a polyimide
    B) from 0.001 to 20% by weight of iron powder with a particle size of at most 10 μm (d50 value), which is obtainable via thermal decomposition of pentacarbonyliron,
    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%.

## Background
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a national stage application (under 35 U.S.C. §371) of PCT/EP2010/065582, filed Oct. 18, 2010, which claims benefit of European application 09174173.6, filed Oct. 27, 2009, and European application 10162960.8, filed May 17, 2010.
The invention relates to thermoplastic molding compositions, comprising

    A) from 10 to 99.999% by weight of a polyamide,
    B) from 0.001 to 20% by weight of iron powder with a particle size of at most 10 μm (d50 value), which is obtainable via thermal decomposition of pentacarbonyliron,
    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 the production of fibers, foils, and moldings of any kind, 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 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 the risk that these will fail. As an alternative, an improved HAR can also permit the use of the components at higher temperatures.
The use of elemental iron powder in polyamides is disclosed in DE-A 26 02 449, JP-A 09/221590, JP-A 2000/86889 (in each case as filler), JP-A 2000/256 123 (as decorative addition), and also WO 2006/074912 and WO 2005/007727 (stabilizers).
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 inadequate, in particular over prolonged periods of thermal stress.
The surface of the moldings is not entirely satisfactory, since heat-aging causes porosity, and also blistering.
The more recent EP application, file reference: 08171803.3, proposes combinations of polyethyleneimines with iron powder to improve HAR.
It was therefore an object of the present invention to provide thermoplastic polyamide molding compositions which have improved HAR and have a good surface after heat-aging, and also good mechanical properties. The intention is to improve processing by means of welding processes, in particular for vibration welding and laser welding processes.
The molding compositions defined in the introduction have accordingly been found. Preferred embodiments are given in the dependent claims.
The molding compositions of the invention comprise, as component A), from 10 to 99.999% by weight, preferably from 20 to 98% by weight, and in particular from 25 to 94% by 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 25° C. to ISO 307.
Preference is given to semicrystalline or amorphous resins with a molecular weight (weight average) of at least 5 000, described by way of example in the following U.S. Pat. Nos. 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.
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.
Dicarboxylic acids which may be used are alkanedicarboxylic acids having 6 to 12, in particular 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.
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-amino-cyclohexyl)propane, and 1,5-diamino-2-methylpentane.
Preferred polyamides are polyhexamethyleneadipamide, polyhexamethylene-sebacamide, 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).
Other suitable polyamides are obtainable from w-aminoalkyinitriles, e.g. amino-capronitrile (PA 6) and adipodinitrile with hexamethylenediamine (PA 66) via 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 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 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 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/6I/MXD6).
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 comprised:
AB Polymers:
PA 4 Pyrrolidone
PA 6 ε-Caprolactam
PA 7 Ethanolactam
PA 8 Caprylolactam
PA 9 9-Aminopelargonic acid
PA 11 11-Aminoundecanoic acid
PA 12 Laurolactam
AA/BB polymers:
PA 46 Tetramethylenediamine, adipic acid
PA 66 Hexamethylenediamine, adipic acid
PA 69 Hexamethylenediamine, azelaic acid
PA 610 Hexamethylenediamine, sebacic acid
PA 612 Hexamethylenediamine, decanedicarboxylic acid
PA 613 Hexamethylenediamine, undecanedicarboxylic acid
PA 1212 1,12-Dodecanediamine, decanedicarboxylic acid
PA 1313 1,13-Diaminotridecane, undecanedicarboxylic acid
PA 6T Hexamethylenediamine, terephthalic acid
PA 9T 1,9-Nonanediamine, terephthalic acid
PA MXD6 m-Xylylenediamine, adipic acid
AA/BB Polymers:
PA 6I Hexamethylenediamine, isophthalic acid
PA 6-3-T Trimethylhexamethylenediamine, terephthalic acid
PA 6/6T (see PA 6 and PA 6T)
PA 6/66 (see PA 6 and PA 66)
PA 6/12 (see PA 6 and PA 12)
PA 66/6/610 (see PA 66, PA 6 and PA 610)
PA 6I/6T (see PA 6I and PA 6T)
PA PACM 12 Diaminodicyclohexylmethane, laurolactam
PA 6I/6T/PACM as PA 6I/6T+diaminodicyclohexylmethane
PA 12/MACMI Laurolactam, dimethyldiaminodicyclohexylmethane, isophthalic acid
PA 12/MACMT Laurolactam, dimethyldiaminodicyclohexylmethane, terephthalic acid
PA PDA-T Phenylenediamine, terephthalic acid
The molding compositions of the invention comprise, as component B), 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 μm (d50 value), which is obtainable via thermal decomposition of pentacarbonyliron.
Iron occurs in a number of allotropes:

    α-Fe (ferrite) forms space-centered cubic lattices, is magnetizable, dissolves a small amount of carbon, and occurs in pure iron up to 928° C. At 770° C. (Curie temperature) it loses its ferromagnetic properties and becomes paramagnetic; iron in the temperature range from 770 to 928° C. is also termed β-Fe. At normal temperature and at a pressure of at least 13 000 MPa, α-Fe becomes what is known as ε-Fe with a reduction of about 0.20 cm3/mol in volume, whereupon density increases from 7.85 to 9.1 (at 20 000 MPa).
    2. γ-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 1398° C.
    3. δ-Fe, space-centered, exists at from 1398° C. to the melting point of 1539° C.


Metallic iron is generally silver-white, density 7.874 (heavy metal), m.p. 1539° C., boiling point 2880° C.; specific heat (from 18 to 100° C.) about 0.5 g−1 K−1, tensile strength from 220 to 280 N/mm2. The values apply to chemically pure iron.
Industrial production of iron uses smelting of iron ores, iron slags, calcined pyrites, or 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 preferably spherical shape, therefore being spherical or almost spherical (another term used being spherolitic).
Preferred iron powder has the particle size distribution described below, and the particle size distribution here is determined by means of laser scattering in a highly diluted aqueous suspension (e.g. using a Beckmann LS13320). The particle size (and distribution) described hereinafter can optionally be obtained via grinding and/or sieving.
dxx here means that XX % of the total volume of the particles is smaller than the stated value.

    d50 values: at most 10 μm, preferably from 1.6 to 8 μm, in particular from 2.9 to 7.5 μm, very particularly from 3.4 to 5.2 μm
    d10 values: preferably from 1 to 5 μm, in particular from 1 to 3 μm, and very particularly from 1.4 to 2.7 μm
    d90 values: preferably from 3 to 35 μm, in particular from 3 to 12 μm, and very particularly from 6.4 to 9.2 μm.


Component B) preferably has iron content of from 97 to 99.8 g/100 g, preferably from 97.5 to 99.6 g/100 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 and especially from 0.4 to 1.1 g/100 g. This C content in the preferred iron powders corresponds to powders which are not reduced with hydrogen after the thermal decomposition process. The C content is usually determined by combustion of the sample in a stream of oxygen and then using IR to detect the resultant CO2 gas (by means of a Leco CS230 or CS-mat 6250 from Juwe) by a method based on ASTM E1019.
Nitrogen content is preferably at most 1.5 g/100 g, preferably from 0.01 to 1.2 g/100 g. Oxygen content is preferably at most 1.3 g/100 g, preferably from 0.3 to 0.65 g/100 g.
N and O are determined via heating of the specimen to about 2100° C. in graphite furnace. The oxygen obtained from the specimen here is converted to CO and 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 being based on ASTM E1019).
Tap density is preferably from 2.5 to 5 g/cm3, in particular from 2.7 to 4.4 g/cm3. This generally means the density when the powder is, for example, charged to the container and compacted by vibration. Iron powder to which further preference is given can have been surface-coated with iron phosphate, with iron phosphite, or with SiO2.
BET surface area to DIN ISO 9277 is preferably from 0.1 to 10 m2/g, in particular from 0.1 to 5 m2/g, preferably from 0.2 to 1 m2/g and in particular from 0.4 to 1 m2/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, 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.
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 C1) that may be mentioned are carbon fibers, glass fibers, glass beads, amorphous silica, calcium silicate, calcium metasilicate, magnesium carbonate, kaolin, chalk, powdered quartz, mica, barium sulfate, and feldspar, and the amounts of these that can be used are from 1 to 50% by weight, in particular from 1 to 40% by weight, preferably from 10 to 40% by weight.
Preferred fibrous fillers that may be mentioned are carbon fibers, aramid fibers, and 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 improve compatibility with the thermoplastic.
Suitable silane compounds have the general formula:

(X—(CH2)n)k—Si—(O—CmH2m+1)4-k 

where the definitions of the substituents are as follows:

X NH2—,





HO—,

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 1 to 3, preferably 1.

Preferred silane compounds are aminopropyltrimethoxysilane, aminobutyltrimethoxy-silane, aminopropyltriethoxysilane and aminobutyltriethoxysilane, and also the corresponding silanes which comprise a glycidyl group as substituent X.
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 C)).
Long glass fibers are also suitable as component C1), and can be used in the form of roving. The glass fibers used in the form of roving in the invention have a diameter of from 6 to 20 μm, preferably from 10 to 18 μm, and the cross section of the glass fibers here is round, oval, or polygonal. In particular, the invention uses E glass fibers. However, it is also possible to use any other types of glass fiber, e.g. A, C, D, M, S, or R glass fibers, or any desired mixture thereof, or a mixture with E glass fibers. The L/D (length/diameter) ratio is preferably from 100 to 4000, in particular from 350 to 2000, and very particularly from 350 to 700.
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 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 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 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.
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.
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.
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 acid (a mixture of fatty acids having from 30 to 40 carbon atoms).
The aliphatic alcohols can be monohydric to tetrahydric. Examples of alcohols are n-butanol, n-octanol, stearyl alcohol, ethylene glycol, propylene glycol, neopentyl glycol, pentaerythritol, preference being given to glycerol and pentaerythritol.
The aliphatic amines can be mono- to tribasic. Examples of these are stearylamine, ethylenediamine, propylenediamine, hexamethylenediamine, di(6-aminohexyl)amine, particular preference being given to ethylenediamine and hexamethylenediamine. Preferred esters or amides are correspondingly glycerol distearate, glycerol tristearate, ethylenediamine distearate, glycerol monopalmitate, glycerol trilaurate, glycerol monobehenate, and pentaerythritol tetrastearate.
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 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.
Preferred salts of monovalent copper used are cuprous acetate, cuprous chloride, cuprous bromide, and cuprous iodide. The materials comprise these in amounts of from 5 to 500 ppm of copper, preferably from 10 to 250 ppm, based on polyamide.
The advantageous properties are in particular obtained if the copper is present with molecular distribution in the polyamide. 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 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.
Suitable polyamides for the concentrate are homopolyamides and copolyamides, in particular nylon-6 and nylon-6,6.
Suitable sterically hindered phenols C3) are in principle all of the compounds which have a phenolic structure and which have at least one bulky group on the phenolic ring.
It is preferable to use, for example, compounds of the formula




where:

R1 and R2 are an alkyl group, a substituted alkyl group, or a substituted triazole group, and where the radicals R1 and R2 may be identical or different, and R3 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 (U.S. Pat. No. 4,360,617).
Another group of preferred sterically hindered phenols is provided by those derived from substituted benzenecarboxylic acids, in particular from substituted benzenepropionic acids.
Particularly preferred compounds from this class are compounds of the formula




where R4, R5, R7, and R8, independently of one another, are C1-C8-alkyl groups which themselves may have substitution (at least one of these being a bulky group), and R8 is a divalent aliphatic radical which has from 1 to 10 carbon atoms and whose main chain may also have C—O bonds.

Preferred compounds corresponding to these formulae are




All of the following should be mentioned as examples of sterically hindered phenols:
2,2′-methylenebis(4-methyl-6-tent-butylphenol), 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), pentaerythrityl tetrakis[3-(3,5-di-tert-butyl-4-hydroxy-phenol)propionate], distearyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 2,6,7-trioxa-1-phosphabicyclo[2.2.2]oct-4-ylmethyl 3,5-di-tert-butyl-4-hydroxyhydro-cinnamate, 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-hydroxy-benzyl)benzene, 4,4′-methylenebis(2,6-di-tert-butylphenol), 3,5-di-tert-butyl-4-hydroxy-benzyldimethylamine.
Compounds which have proven particularly effective and which are therefore used with preference are 2,2′-methylenebis(4-methyl-6-tert-butylphenyl), 1,6-hexanediol bis(3,5-di-tert-butyl-4-hydroxyphenyl]propionate (Irganox® 259), pentaerythrityl tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and also N,N′-hexamethylene-bis-3,5-di-tert-butyl-4-hydroxyhydrocinnamide (Irganox® 1098), and the product Irganox® 245 described above from Ciba Geigy, which has particularly good suitability.
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).
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.
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 1.5% by weight, of a nigrosin.
Nigrosins 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), 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.
Nigrosins are obtained industrially via heating of nitrobenzene, aniline, and aniline hydrochloride with metallic iron and FeCl3 (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).
Further details concerning nigrosins can be found by way of example in the electronic encyclopedia Rompp Online, Version 2.8, Thieme-Verlag Stuttgart, 2006, keyword “Nigrosin”.
Examples of other conventional additives C) are amounts of up to 25% by weight, 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, 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), 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.
Preferred types of such elastomers are those known as ethylene-propylene (EPM) and ethylene-propylene-diene (EPDM) rubbers.
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 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 alkenyl-norbornenes, such as 5-ethylidene-2-norbornene, 5-butylidene-2-norbornene, 2-methallyl-5-norbornene and 2-isopropenyl-5-norbornene, and tricyclodienes, such as 3-methyltricyclo[5.2.1.02,6]-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.
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.
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 monomers comprising dicarboxylic acid derivatives or 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 II or III or IV




where R1 to R9 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 number from 0 to 5.

The radicals R1 to R9 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.
Preferred compounds of the formulae I, II 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 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 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,
    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 and/or 2-ethylhexyl acrylate.


Other preferred (meth)acrylates are the methyl, ethyl, propyl, isobutyl and tert-butyl esters.
Comonomers which may be used alongside these are vinyl esters and vinyl ethers.
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.
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 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 the rubber fraction of the elastomers are acrylates, such as 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 styrene, acrylonitrile, vinyl ethers and with other acrylates or methacrylates, such as methyl methacrylate, methyl acrylate, ethyl 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 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, methacrylonitrile, α-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 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




where the substituents can be defined as follows:

    R10 is hydrogen or a C1-C4-alkyl group,
    R11 is hydrogen, a C1-C8-alkyl group or an aryl group, in particular phenyl,
    R12 is hydrogen, a C1-C10-alkyl group, a C6-C12-aryl group, or —OR13,
    R13 is a C1-C8-alkyl group or a C6-C12-aryl group, which can optionally have substitution by groups that comprise O or by groups that comprise N,
    X is a chemical bond, a C1-C10-alkylene group, or a C6-C12-arylene group, or






    Y is O—Z or NH—Z, and
    Z is a C1-C10-alkylene or C6-C12-arylene group.


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, (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 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 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 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.
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 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 U.S. Pat. No. 4,148,846.
The proportion of these crosslinking monomers in the impact-modifying polymer is 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 structure:












Type
Monomers for the core
Monomers for the envelope







I
1,3-butadiene, isoprene, n-butyl
styrene, acrylonitrile, methyl



acrylate, ethylhexyl acrylate, or
methacrylate



a mixture of these


II
as I, but with concomitant use of
as I



crosslinking agents


III
as I or II
n-butyl acrylate, ethyl acrylate,




methyl acrylate, 1,3-butadiene,




isoprene, ethylhexyl acrylate


IV
as I or II
as I or III, but with concomitant




use of monomers having reactive




groups, as described herein


V
styrene, acrylonitrile, methyl
first envelope composed of



methacrylate, or a mixture of
monomers as described under I



these
and II 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 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 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.
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, 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 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.
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.
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.
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.
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 apparatus, such as screw-based extruders, Brabender mixers, or Banbury mixers, and then extruding the same. 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.
In another preferred mode of operation, components B) and also optionally C) can be mixed with a prepolymer, compounded, and pelletized. The resultant pellets are then 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 long glass fiber-reinforced polyamide molding compositions of the invention can be produced by the known processes for the production of elongate long-fiber-reinforced pellets, in particular via pultrusion processes, where the continuous fiber strand (roving) is completely saturated by the polymer melt and then cooled and chopped. The elongate long-fiber-reinforced pellets thus obtained, the pellet length of which is preferably from 3 to 25 mm, in particular from 5 to 14 mm, can be further processed to give moldings by the usual methods of processing (e.g. injection molding, compression molding).
The preferred L/D ratio of the pellets after pultrusion is from 2 to 8, in particular from 3 to 4.5.
Particularly good properties can be achieved in the molding by using non-aggressive processing methods. “Non-aggressive” in this context especially means substantial avoidance of excessive fiber breakage and the attendant severe reduction of fiber length. In the case of injection molding this means that it is preferable to use screws with large diameter and low compression ratio, in particular smaller than 2, and generously dimensioned nozzle channels and feed channels. A requirement supplementary to this is that high cylinder temperatures are used for rapid melting (contact heating) of the elongate pellets, and that the fibers are not excessively comminuted by overexposure to shear. When these measures are applied, the invention gives moldings which have higher average fiber length than comparable moldings produced from short-fiber-reinforced molding compositions. An additional improvement of properties is therefore achieved, in particular in tensile modulus of elasticity, ultimate tensile strength, and notched impact resistance.
The usual fiber length after processing of the molding, e.g. via injection molding, is from 0.5 to 10 mm, in particular from 1 to 3 mm.
The thermoplastic molding compositions of the invention feature good processability, in particular with welding methods such as vibration welding or laser welding, 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 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 modules, microelectronic components, coils, I/O plug connectors, plugs for printed circuit boards (PCBs), plugs for flexible printed circuits (FPCs), plugs for flexible integrated circuits (FFCs), high-speed plug connectors, terminal strips, connector plugs, device connectors, cable-harness components, circuit mounts, circuit-mount components, three-dimensionally injection-molded circuit mounts, electrical connectors, 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-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.
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.


EXAMPLES
I. Study of Various Iron Powders
The following components were used:
Component A/1
Nylon-6,6 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 from BASF SE was used.)
Component N2
Polyamide composed of m-xylylenediamine and adipic acid (molar ratio 1:1) with IV=65 ml/g (Ultramid® X17 from BASF SE)
Component A/3
PA6/66 (80:20) with IV 176 ml/g (Ultramid® C31-01)
Component A/4
PA 6 with IV 148 ml/g to ISO 307 (Ultramid® B27)
Component B/1
All iron powders have CAS No. 7439-89-6. For determination of Fe, C, N, and O content, see description pages 5 and 6.


















Fe
g/100 g
at least
IR detection





97.7



C
g/100 g
at most
IRS





1.0



N
g/100 g
at most
TCD





1.0



O
g/100 g
at most
IRS





0.6










Particle size distribution: (laser scattering with Beckmann LS13320)
d10 from 1.4 to 2.7 μm
d50 from 2.9 to 4.2 μm
d90 from 6.4 to 9.2 μm
BET surface area 0.44 m2/g (DIN ISO 9277)
Component B/2


















Fe
g/100 g
min. 97.8




C
g/100 g
0.6-0.9



N
g/100 g
0.6-0.9



O
g/100 g
0.45-0.65



Particle size



distribution:



d10
μm
max. 1.0



d50
μm
max. 2.0



d90
μm
max. 3.0



Tap density
g/cm3
3.4-4.0
Method based on






ASTM B527










BET surface area: 0.93 m2/g (DIN ISO 9277)
Component B/3

















Fe
g/100 g
min. 99.5



C
g/100 g
max. 0.05



N
g/100 g
max. 0.01



O
g/100 g
max. 0.4



SiO2 coating
mg/kg
0.08-0.12



Tap density
g/cm3
 3.9-4.4



Particle size distribution:



d10
μm
max. 3



d50
μm
max. 6



d90
μm
max. 12










BET surface area: 0.32 m2/g (DIN ISO 9277)
Component B/4

















Fe
g/100 g
min. 97.2



FePO4 coating
g/100 g
ca. 0.5



C
g/100 g
max. 1.1



N
g/100 g
max. 1.2



O
g/100 g
max. 0.6



Particle size distribution:



d50
μm
3.4-4.5










BET surface area: 0.44 m2/g (DIN ISO 9277)
Component B/5

















Fe
g/100 g
min. 88



C
g/100 g
0.4-0.8



O
g/100 g
max. 1.2



N
g/100 g
max. 0.2



P coating
g/100 g
8.0-11.0



Particle size distribution:



d10
μm
max. 3



d50
μm
max. 6



d90
μm
max. 18



Tap density
g/cm3
2.7-3.3










BET surface area: 0.89 m2/g (DIN ISO 9277)
Component B/6
Masterbatch composed of 25% of B/1 in polyethylene
Component B/7
Masterbatch composed of 75% of B/1 in polyethylene
Component B/1 Comp
Shelfplus 02 2400 from Ciba Spezialitätenchemie GmbH (20% strength Fe powder masterbatch in polyethylene, d50=30 μm)
BET surface area to DIN ISO 9277: 20 m2/g
C content: 0.012 g/100 g
Component C/1
Glass fibers
Component C/2a
Calcium stearate
Component C/3
CuI/KI in ratio 1:4 (20 strength masterbatch in PA6)
Component C/4
40% strength PA6 masterbatch with nigrosin
Component C/5
Na pyrophosphate
Component C/6
NaCl
Component C/1 Comp
Fe2O3, spec. surface area to DIN 66131 (BET) from 6.8 to 9.2 m2/g
(Bayoxid E8708 from Lanxess)
Component C/2 Comp
Fe3O4, BET 0.23 m2/g (Minelco Magni F50 from Minelco GmbH)
Component C/7
















Lupasol ®
WF



Mw
25 000



Prim./sec./tert. amines
1/1.2/0.76










Lupasol®=registered trademark of BASF SE
The primary/secondary/tertiary amines ratio was determined by means of 13C NMR spectroscopy.
The molding compositions were produced in a ZSK 30 with throughput 10 kg/h and a flat temperature profile at about 260° C.
The following measurements were made:
Tensile to ISO 527, mechanical properties prior to and after heat-aging at 220° C. in a convection oven;
IV: c=5 g/l in 96% strength sulfuric acid, to ISO 307
The injection pressure determined was the pressure at the changeover point during the injection molding process for tensile specimens to ISO 527.
The tables give the constitutions of the molding compositions and the results of the measurements.







TABLE 1





Constitutions



























A/1 [%












Ex.
by wt.]
A/2
A/3
A/4
C/2a
C/1
C/4
C/3
C/5
C/6
C/7





1
67.76



0.35
30
1.9


2
63.75



0.35
30
1.9


3
66.76



0.35
30
1.9


4
67.46



0.35
30
1.9
0.3


5
63.45



0.35
30
1.9
0.3


6
66.46



0.35
30
1.9
0.3


7
66.96



0.35
30
1.9
0.3


8
66.46



0.35
30
1.9
0.3


9
66.46



0.35
30
1.9
0.3


10
66.46



0.35
30
1.9
0.3


11
66.35



0.35
30
1.9
0.3


12
66.07



0.35
30
1.9
0.3


13
66.07



0.35
30
1.9
0.3


14
65.50



0.35
30
1.9
0.3
0.5
0.5


15
65.96



0.35
30
1.9
0.3


0.5


16
66.46



0.35
30
1.9
0.3


0.5


17
56.45

10.0

0.35
30
1.9
0.3


18
46.45

20.0

0.35
30
1.9
0.3


19
61.46
5.0


0.35
30
1.9
0.3


20
63.46



0.35
30
1.9
0.3


21
66.12



0.35
30
1.9
0.3


22
56.45


10.0
0.35
30
1.9
0.3


23
46.45


20.0
0.35
30
1.9
0.3





















B/1





C/1
C/2




Ex.
comp
B/1
B/2
B/3
B/4
B/5
comp
comp
B/6
B/7





1


2
4.0


3

1.0


4


5
4.0


6

1.0


7

0.5


8


1.0


9



1.0


10




1.0


11





1.1


12






1.4


13







1.4


14

1.0


15

1.0


16

0.5


17

1.0


18

1.0


19

1.0


20








4


21









1.3


22

1.0


23

1.0





Example 5 for comparison: WO 2005/7727 and WO 2006/74912 - examples 12 and 13 for comparison: EP 1846506













TABLE 2





Test results


















Injection













pressure

Modulus of elasticity
Tensile strength (tensile stress at break)





















Ex.
(bar)
IV
0 h
500 h
750 h
1000 h
1250 h
1500 h
0 h
500 h
750 h
1000 h
1250 h
1500 h





1
391
153.9
9686
8564
5886
2968


188
82
42
9


2
394
155.8
9656
10680
10119
9139


185
98
86
78


3
387
157.9
9589
10092
9477
8067


182
161
133
109


4
407
153.0
9663
9551
7386
brittle


191
97
55
brittle


5
417
144.8
9721
10764
9979
8202
7340
6090
190
94
76
76
76
71


6
369
148.0
9702
10721
10656
10342
10282
9607
183
159
151
151
142
125


7
394
149.0
9644
10689
10521
10514
10592
10119
188.5
160
151
148
149
140


8
340
149.2
9606
10509
10384
10156
10235
9714
182
159
154
148
144
131


9
341
124.7
9472
10528
10533
10619


180
151
147
138


10
354
145.6
9719
10743
10386
10280


186
164
154
150


11
321
134.2
9572
10491
10147
9871
9250
8448
175
165
153
133
119
102


12
346
146.7
9588
10248
9666
Test not


168
137
120
Test not








poss.





poss.


13
335
141.8
9695
10354
9934
Test not


171.5
144
129
Test not








poss.





poss.


14
267
143.3
10148
11055
10793
9858


190.5
104
94
88


15
268
136.2
9897
10865
10643
10726


177
132
127
109


16
273
129.3
10167
10966
10883
10453
10979
10900
184.5
136
137
133
132
139


17
347
138.9
9399
10497
10410
10435
10418
10611
175
163
166
125
168
173


18
354
139.6
9392
10291
10237
10272
10225
10277
171.5
167
169
129
171
171


19
321
128.1
10009
10902
10764
10492
10117
9719
191
176
170
133
144
127


20
373
128.1
9598
10340
10280
10123
9738
9623
172
158
133
102
133
127


21
365
144.2
9749
10490
10466
10341


182.5
161
147
100


22
314
142.2
9831
10927
10535
10774

10640
185
180
178
178

177


23
367
139.6
9665
10889
10658
10630

10792
183
179
180
183

185












Elongation at break (tensile strain at break)













Ex.
0 h
500 h
750 h
1000 h
1250 h
1500 h





1
3.6
1.2
1.0
0.4


2
3.2
1.3
1.0
1.1


3
3.3
2.2
1.2
1.7


4
3.6
1.2
1.8
brittle


5
3.2
1.3
1.0
1.3
1.3
1.3


6
3.4
1.9
1.8
1.8
1.7
1.6


7
3.5
2.0
1.8
1.8
1.7
1.6


8
3.3
2.0
1.9
1.9
1.8
1.7


9
3.5
1.9
1.9
1.7


10
3.3
2.1
1.9
1.9


11
3.0
2.1
1.9
1.7
1.6
1.5


12
2.6
1.7
1.5
Test not






poss.


13
2.7
1.8
1.6
Test not






poss.


14
2.9
1.4
1.3
1.3


15
2.6
1.4
1.4
1.2


16
2.7
1.5
1.5
1.3
1.5
1.6


17
3.4
2.1
2.2
1.4
2.3
2.4


18
3.5
2.2
2.3
1.5
2.6
2.6


19
3.1
2.1
2.1
1.5
1.8
1.6


20
3.1
2.1
1.7
1.1
1.7
1.7


21
3.2
2.0
1.8
1.1


22
3.4
2.3
2.4
2.3

2.3


23
3.6
2.3
2.5
2.7

2.6









II. PA 46 as Matrix
The components corresponded to part I, but PA 46 with IV: 151 ml/g (Stanyl® from DSM) was used as component A/5 and ethylenebisstearylamide was used as component C/2b.
















TABLE 3













B/1




A/5
C/1
C/2b
C/4
C/3
C/5
C/6
comp
B/1


Ex. No.
(%)
(%)
(%)
(%)
(%)
(%)
(%)
(%)
(%)
























1
64.46
30
0.34
1.9
0.3
0
0
3.0
0


comp


1
65.75
30
0.34
1.9
0.3
0.5
0.46
0
0.75
















TABLE 4







Heat-aging at 200° C.












Ex. No.
0 h
250 h
750 h
1250 h
1500 h












Modulus of elasticity












1
  9800
10 200
  9900
9000
8800


comp


1
10 000
10 500
10 000
8500
7900









Tensile strength (tensile stress at break)












1
  195
  169
  114
82
74


comp


1
  197
  178
  125
89
76









Elongation at break (tensile strain at break)












1
    3.0
    2.1
    1.3
1.0
1.0


comp


1
    2.7
    2.2
    1.5
1.3
1.4
















TABLE 5







Heat-aging at 220° C.












Ex. No.
0 h
250 h
750 h
1250 h
1500 h












Modulus of elasticity












1
  9800
10 200
  9900
  9800
  9800


comp


1
10 000
10 400
10 500
10 300
10 500









Tensile strength (tensile stress at break)












1
  195
  125
  95
  86
  79


comp


1
  197
  155
  137
  130
  116









Elongation at break (tensile strain at break)












1
    3.0
    1.5
    1.2
    1.1
    1.0


comp


1
    2.7
    1.8
    1.6
    1.4
    1.3









III. Long-Glass Fiber-Reinforced Compositions
The components corresponded to I., but a glass fiber roving with Ø 17 μm was used as component C/8.
The molding compositions were produced as follows:














1)
Pultrusion conditions:




Temperature setting for extruder
285° C.



Impregnation chamber
290° C.



Preheating of roving
180° C.



Take-off speed
9 to 12 m/min



Pellet length
12 mm



Pellet L/D
 4


2)
Glass fiber L/D after injection molding
120









The test specimens used for determination of properties were obtained by means of injection molding (injection temperature 280° C., melting point 80° C.).














TABLE 6






A/1
A/3
C/2a
C/8
C/4
C/3
B/6


Ex. No.
(%)
(%)
(%)
(%)
(%)
(%)
(%)







1
33.45
10.0
0.35
50
1.9
0.3
4


2
37.45
10.0
0.35
50
1.9
0.3
0


comp


3
53.45
10.0
0.35
30
1.9
0.3
4


4
57.45
10.0
0.35
30
1.9
0.3
0


comp
















TABLE 7







Heat aging at 200° C.













Ex. No.
0 h
500 h
1000 h
1500 h
2000 h
2500 h












Modulus of elasticity













1
16 051
17 235
16 698
16 835
16 096
16 118


2
16 425
17 335
16 998
16 844
15 160
11 538


comp


3
10 274
11 156
10 728
10 888
10 294
10 475


4
10 122
11 472
10 970
10 363
  8005
Not


comp





measured









Tensile strength (tensile stress at break)













1
  243
  212
  245
  208
  203
  192


2
  268
  188
  232
  178
  128
  84


comp


3
  180
  167
  179
  174
  167
  155


4
  187
  176
  166
  115
  58
Not


comp





measured









Elongation at break (tensile strain at break)













1
    2.0
    1.5
    1.9
    1.5
    1.6
    1.5


  2V
    2.3
    1.3
    1.7
    1.3
    1.0
    0.9


3
    2.0
    1.8
    1.9
    1.9
    1.9
    1.8


  4V
    2.1
    1.9
    1.7
    1.3
    0.8
Not








measured
















TABLE 8







Heat aging at 220° C.













Ex. No.
0 h
500 h
1000 h
1500 h
2000 h
2500 h












Modulus of elasticity













1
16 051
16 958
17 419
16 142
16 984
15 707


2
16 425
17 475
10 750
  836
Not
Not


comp




measured
measured


3
10 274
10 648
11 106
11 001
10 922
10 393


4
10 122
11 094
10 465
  5932
Not
Not


comp




measured
measured









Tensile strength (tensile stress at break)













1
  243
  260
  218
  228
  178
  114


2
  268
  249
  53
    0.9
Not
Not


comp




measured
measured


3
  180
  179
  169
  170
  152
  112


4
  187
  181
  115
  45
Not
Not


comp




measured
measured









Elongation at break (tensile strain at break)













1
    2.0
    2.1
    1.6
    1.8
    1.2
    0.8


2
    2.3
    1.9
    0.6
   0
Not
Not


comp




measured
measured


3
    2.0
    1.9
    1.8
    1.8
    1.6
    1.2


4
    2.1
    1.9
    1.3
    0.9
Not
Not


comp




measured
measured









IV. Vibration Welding
The components used were the same as in I.














TABLE 9






A/1
A/3
C/1
C/2a
C/4
C/3
B/1


Ex. No.
(%)
(%)
(%)
(%)
(%)
(%)
(%)






















1
67.45
0
30
0.35
1.9
0.3
0


comp


1
66.45
0
30
0.35
1.9
0.3
1.0


2
46.45
20
30
0.35
1.9
0.3
1.0
















TABLE 10







Vibration-welded moldings


Mechanical properties after heat-aging at 220° C.












Ex. No.
0 h
500 h
1000 h













Tensile strength (MPa)



(tensile stress)












1 comp
77
24
3



1
78
26
15



2
77
55
35









Bending strength (MPa)



(flexural stress)












1 comp
127
38
1



1
126
51
26



2
136
115
102










Description of Test: Vibration Welding of Engineering Plastics

Test Specimens

Test specimens in the form of sheets are used in order to study the effect of material on the welding process and the quality of the joint. Use of a film gate across the entire width of the injection molding achieves uniform melt orientation and avoids inhomogeneity. The thickness of the injection-molded sheets is 4 mm, and the sprue region is removed by sawing so that the dimensions of the sheets are 110 mm×110 mm. A circular saw is then used to halve the sheets in the direction of injection, giving them final dimensions of about 55 mm×110 mm. In the welding processes that follow, the external (unsawn) edges are welded. The resultant joint area is 440 mm2. The standard sheet serves as geometrically simple test specimen for analyzing effects of materials and/or of parameters on the quality of the joint. The simple shape of the sheet permits secure fixing in the welding tool, because the entire length is supported on both sides in the tool.
Welding Machine
An M-102 H ultrasound vibration welding machine from Branson is used to carry out the welding tests.
Welding Process
The form of vibration used to weld the sheets is “linear-longitudinal”. The mode used for the vibration welding studies is “displacement-controlled welding with constant pressure level”. The tests take place at constant amplitude of 0.9 mm and constant welding pressure of 1.6 MPa. Vibration frequency used is the resonance frequency, which is about 220 Hz. Two welding tests are carried out for each parameter/material setting.
Mechanical Testing
The flat specimens needed for the tensile and flexural tests are cut with a circular saw to a width of 25 mm perpendicularly with respect to the welded area. Three specimens of a welded sheet of each parameter/material setting are tested. The welding bead is not removed here.
V: Semiaromatic Polyamide (6T/6I/MXD.T/I)







TABLE 11







Constitutions (% by wt.)



















Ex. 
A/6
A/4
B/1
C/1
C/2
C/3
C/4
C/5
C/6
C/7
C/8
C/9





1
64.10


35.00
0.05
0.35





0.50


2
58.85


35.00
0.05
0.35
1.25
4.00



0.50


3
59.45


35.00
0.05
0.35

4.00
0.65


0.50


4
59.80


35.00
0.05
0.35

4.00


0.30
0.50


5
49.80
10.00

35.00
0.05
0.35

4.00


0.30
0.50


6
55.80

4.00
35.00
0.05
0.35

4.00


0.30
0.50


7
45.80
10.00
4.00
35.00
0.05
0.35

4.00


0.30
0.50


8
45.30
10.00
4.00
35.00
0.05
0.35

4.00

0.50
0.30
0.50





A/6


Semiaromatic polyamide based on 6.T/6.1/MXD.T/I having 64% by wt. of 6.T units, 29% by wt. of 6.I and 7% by wt. of MXD.T/MXD.I units. IV measured on the base polymer: 90 ml/g (0.5% by wt. in 96% sulfuric acid at 25° C., ISO 307).


T = terephthalic acid


I = isophthalic acid


MXD = m-xylylenediamine


A/4 (see I.)


Nylon-6 with IV 148 ml/g (ISO 307; Ultramid ® B27).


B/1


Masterbatch made of 25% by wt. of B/1 (see I.) in nylon-6,6.


C/1


Glass fibers with 10 μm average diameter


C/2


Talc powder


C/3


Partially oxidized polyethylene wax (acid number 15-19 mg KOH/g; melt viscosity at 120° C.: 350-470 mm2/s ((DGF M-III 8); Luwax ® OA5)


C/4


Mixture of various additives (parts based on weight):


1 part of N,N′-hexane-1,6-dihylbis(3-(3,5-di-tert-butyl-4-hydroxyphenylpropionamide)) (Irganox ® 1098),


1 part of high-molecular-weight hindered amine having the following structure (Chimassorb ® 2020):





1 part of 2,2′-methylene bis(6-(2H-benzotriazol-2-yl)-4-1,1,3,3-tetramethylbutyl)phenol) (Tinuvin ® 360),


4 parts of a carbon black masterbatch (30% by weight in LDPE)


C/5


Ethylene-butyl acrylate rubber, functionalized with maleic anhydride (Fusabond ® NM 598D)


C/6


4,3′-Bis(alpha, alpha-dimethylbenzyl)diphenylamine (Naugard ® 445)


C/7


Polyethyleneimine with Mw~25 000 g/mol and with a ratio of primary:secondary:tertiary amine of 1:1.20:0.76 (Lupasol ® WF)


C/8


CuI/KI in a ratio of 1:4


C/9


Calcium montanate













TABLE 12







Heat-aging in convection oven at 235° C.












Relative change in weight of



a tensile specimen in comparison



with initial value (0 h)/%














Ex. No.
0 h
250 h
500 h
750 h
1000 h







1
100
90.6
77.0
65.8
64.0



2
100
97.8
90.1
79.0
68.9



3
100
95.5
91.7
68.5
64.6



4
100
97.2
90.1
79.7
71.8



5
100
97.1
96.1
93.7
90.2



6
100
98.5
96.5
91.2
85.0



7
100
99.5
97.8
97.4
96.9



8
100
98.0
97.9
97.4
96.9













Modulus of elasticity/MPa












Ex. No.
0 h
250 h
500 h
750 h
1000 h





1
13 300
14 000
—a)
—a)
—a)


2
12 700
12 640
—a)
—a)
—a)


3
12 000
12 300
—a)
—a)
—a)


4
11 900
12 530
12 750
12 520
—a)


5
11 900
12 240
13 230
12 760
12 870


6
11 000
11 700
12 080
10 970
10 840


7
10 900
11 740
12 700
11 990
11 850


8
10 900
11 780
12 570
11 960
11 800










a)Highly aged tensile specimens break even at low pressure; no


measurement possible









Tensile strength/MPa














Ex. No.
0 h
250 h
500 h
750 h
1000 h







1
194
70
—a)
—a)
—a)



2
186
92
—a)
—a)
—a)



3
209
60
—a)
—a)
—a)



4
205
98
 56
 45
—a)



5
210
126
124
114
105



6
170
147
131
 93
 81



7
188
207
212
202
198



8
187
202
218
206
198











a)Highly aged tensile specimens break even at low pressure; no


measurement possible









Tensile strain at break/%














Ex. No.
0 h
250 h
500 h
750 h
1000 h







1
2.1
0.5
—a)
—a)
—a)



2
1.8
0.8
—a)
—a)
—a)



3
2.3
0.5
—a)
—a)
—a)



4
2.3
0.9
0.5
0.4
—a)



5
2.4
1.2
1.2
1.1
1.1



6
1.9
1.4
1.3
0.9
0.9



7
2.4
2.2
2.2
2.1
2.1



8
2.3
2.1
2.3
2.2
2.0











a)Highly aged tensile specimens break even at low pressure; no


measurement possible









Impact resistant (Charpy, without



notch)/kJ/m2














Ex. No.
0 h
250 h
500 h
750 h
1000 h







1
40
—a)
—a)
—a)
—a)



2
42
12
—a)
—a)
—a)



3
59
6
—a)
—a)
—a)



4
58
15
7
4
—a)



5
—b)
—b)
—b)
—b)
—b)



6
60
31
22
19
—a)



7
58
51
61
58
65



8
59
41
66
61
44











a)Highly aged specimens break even at low pressure; no measurement


possible


b)Not tested

## Claims

1. A thermoplastic molding composition comprising
A) from 10 to 99.999% by weight of a polyamide,
B) from 0.001 to 20% by weight of iron powder with a particle size of at most 10 μm (d50 value), which is obtained via thermal decomposition of pentacarbonyliron and has a specific BET surface area of from 0.1 to 5 m2/g to DIN ISO 9277,
C) from 0 to 70% by weight of further additives,
where the total of the percentages by weight of components A) to C) does not exceed 100%.

2. The thermoplastic molding composition according to claim 1, in which component B) has a d10 value of from 1 to 5 μm.

3. The thermoplastic molding composition according to claim 1, in which component B) has a d90 value of from 3 to 35 μm.

4. The thermoplastic molding composition according to claim 2, in which component B) has a C content of from 0.05 to 1.2 g/100 g (according to ASTM E1019).

5. The thermoplastic molding composition according to claim 1, in which component B) has a tap density of from 2.5 to 5 g/cm3.

6. The thermoplastic molding composition according to claim 2, in which component B) has a d90 value of from 3 to 35 μm, a tap density of from 2.5 to 5 g/cm3 and component B) has a C content of from 0.05 to 1.2 g/100 g (according to ASTM E1019).

7. The thermoplastic molding composition according to claim 2, in which component B) has been coated with iron phosphate, iron phosphide, or SiO2, on the surface of the particles.

8. The thermoplastic molding composition according to claim 6, in which component B) has been coated with iron phosphate, iron phosphide, or SiO2, on the surface of the particles.

9. A process for the production of fibers, foils, and moldings which comprises utilizing the thermoplastic molding composition according to claim 1.

10. A process for the production of moldings via vibration welding or laser welding which comprises utilizing the thermoplastic molding composition according to claim 1.

11. A fiber, a foil, or a molding, obtained from the thermoplastic molding composition according to claim 1.