Filled polyamide molding compounds, molded articles produced therefrom and use of filled polyamide molding compounds

Abstract

The invention relates to a filled polyamide molding compound having high heat-aging resistance, which, in addition to a specific polyamide mixture, comprises at least one filler, at least one unsubstituted or substituted metallocene and optionally at least one additive. The invention also relates to the use of the polyamide molding compound for producing moldings.

Description

Technical Field

[0001] This invention relates to filled polyamide molding compounds with high heat aging resistance, which, in addition to a specific polyamide mixture, contain at least one filler, at least one unsubstituted or substituted metallocene, and optionally at least one additive. The invention also relates to the use of these polyamide molding compounds in the production of molded articles. Background Technology

[0002] Polyamides can be used as materials for molded parts that will be exposed to elevated temperatures during their service life. Improving the heat aging resistance of polyamides is highly desirable because components subjected to thermal stress can thus achieve a longer service life or a reduced risk of failure. Alternatively, improved heat aging resistance can also allow components to be used at elevated temperatures.

[0003] Thermoplastic polyamides can be used as structural materials for components that will be exposed to elevated temperatures during their service life. Since thermal oxidative damage can occur under these conditions, heat stabilizers are used to delay its occurrence.

[0004] A long-term thermally stable polyamide molding compound is known from EP 2 535 365 A1, wherein a molding compound based on partially aromatic polyamide and caprolactam is introduced, having a copper stabilizer or a mixture of a copper stabilizer and an organic stabilizer.

[0005] Document EP 2 902 444 A1 also relates to long-term heat-stable molding compounds based on partially aromatic polyamides and caprolactam. In this case, long-term heat stability is achieved through the use of organic stabilizers.

[0006] Document EP 1 681 313 A1 also describes long-term stable molding compounds. In this case, long-term thermal stability is achieved by using at least two specific heat stabilizers (e.g., copper iodide and iron oxide) and by using two polyamides with a melt temperature difference of at least 20°C. Summary of the Invention

[0007] Based on this, the object of the present invention is to provide a polyamide molding compound preferably produced therefrom, which is characterized in particular by improved heat aging resistance compared with polyamide molding compounds known from the prior art.

[0008] The stated objective is achieved by the polyamide molding compound according to this application and the molding article according to this application. Other embodiments show advantageous improvements. Use of the polyamide molding compound according to the invention is provided.

[0009] According to the present invention, a polyamide molding compound comprising or composed of the following components (A) to (D) is provided:

[0010] (A) 27% to 89.99% by weight of at least one partially crystalline, partially aromatic polyamide (A1) or a mixture of polyamides, said polyamide mixture comprising:

[0011] At least one partially crystalline, partially aromatic polyamide, and

[0012] At least one caprolactam-containing polyamide having a caprolactam content of at least 50% by weight and being different from the partially crystalline, partially aromatic polyamide (A1).

[0013] The caprolactam content is 5% to 38% by weight relative to the polyamide mixture.

[0014] (B) At least one filler, ranging from 10% to 65% by weight.

[0015] (C) 0.01% to 3.0% by weight of at least one unsubstituted or substituted metallocene,

[0016] (D) At least one additive, ranging from 0% to 35% by weight.

[0017] Components (A) through (D) total 100 by weight.

[0018] Surprisingly, it was found that combining metallocene, particularly ferrocene, with at least one selected partially crystalline, partially aromatic polyamide or a selected mixture of polyamides can result in significantly improved heat aging resistance.

[0019] Furthermore, the ferrocene-containing polyamide molding compound according to the present invention exhibits significantly improved flowability in the spiral flow test. Detailed Implementation

[0020] Terminology Definition

[0021] • Nomenclature and abbreviations of polyamides and their monomers

[0022] In the context of this invention, the term "polyamide" (abbreviated PA) should be understood as an inclusive term; it includes homopolymers and copolymers. The selected names and abbreviations of polyamides and their monomers conform to the definitions in ISO standard 16396-1 (2015, (D)). The abbreviations used herein are used hereinafter as synonyms for the IUPAC names of the monomers. Specifically, the following monomer abbreviations appear in this application: 6 represents 1,6-hexanediamine (CAS No. 124-09-4), T represents terephthalic acid (CAS No. 100-21-0), I represents isophthalic acid (CAS No. 121-95-5), 6 represents 1,6-adipic acid (CAS No. 124-04-9), 6 represents caprolactam (CAS No. 105-60-2), and MACM represents bis(4-amino-3-methyl-cyclohexyl)methane (also known as 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane). Alkane, CAS No. 6864-37-5), TMDC represents bis(4-amino-3,5-dimethyl-cyclohexyl)methane (also known as 3,3',5,5'-tetramethyl-4,4'-diaminodicyclohexylmethane, CAS No. 65962-45-0), PACM represents bis(4-amino-cyclohexyl)methane (also known as 4,4'-diaminodicyclohexylmethane, CAS No. 1761-71-3), BAC represents 1,3-bis(aminomethyl)cyclohexane (also known as... 1,3-Cyclohexanedimethylamine (CAS No. 2579-20-6) and 1,4-bis(aminomethyl)-cyclohexane (also known as 1,4-cyclohexanedimethylamine, CAS No. 2549-93-1) and mixtures thereof, IPD represents isophorone diamine (also known as 3-(aminomethyl)-3,5,5-trimethylcyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, or 5-amino-1,3,5,5-trimethyl-cyclohexane, CAS No. 2855-1) 3-2), MPMD represents 2-methyl-1,5-pentanediamine (also known as 1,5-diamino-2-methylpentane, CAS No. 15520-10-2), MOD represents 2-methyl-1,8-octanediamine (also known as 2-methyloctane-1,8-diamine, CAS No. 148528-05-6), 12 represents dodecanoic acid (also known as 1,10-decanedicarboxylic acid, CAS No. 693-23-2), CHD represents cyclohexanedicarboxylic acid, and 12 represents lactam-12 (also known as laurolactam, CAS No. 947-04-6).

[0023] • General notes about the composition

[0024] The terms “containing” and “comprising” in the claims and specification mean that the possibility of additional components is not excluded. Within the scope of the invention, the term “comprising” is understood to refer to the preferred embodiment of the terms “containing” or “comprising”. If a group is defined as “containing” or “comprising” at least a certain number of components, this should also be understood as disclosing that the group preferably “comprising” those components.

[0025] • Quantity information of monomers

[0026] If the polyamide (A1) contains only diacid and diamine, then its total molar ratio is 50 mol% of all diamines, 50 mol% of all diacids, and the sum of the ratios of diamine and diacid is 100 mol of the polyamide.

[0027] If, in addition to diacids and diamines, the polyamide (A1) or (A2) contains x mol% lactams or ω-amino acids, then relative to 100 mol% of the polyamide, the sum of all diamines is still only (50 - 0.5x) mol% and the sum of all diacids is (50 - 0.5x) mol%.

[0028] Regarding quantitative information about the diacids and diamines in polyamides, it is always applicable that the sum of the mole fractions of all diamines equals the sum of the mole fractions of all diacids.

[0029] • General notes regarding quantity information

[0030] The polyamide molding compound according to the invention comprises or consists of components (A), (B), and (C) and optionally (D); applicable herein is that the sum of components (A), (B), (C), and (D) is mutually complementary to 100% by weight, wherein component (A) consists of component (A1) and optionally component (A2). The definition of the quantity information of individual components (A), (B), (C), and (D) should be understood to mean that each individual component can be selected in any amount within a predefined range, provided that the sum of all components (A), (B), (C), and (D) is 100% by weight.

[0031] • Some aromatic polyamides

[0032] In the context of this invention, a partially aromatic polyamide is a polyamide containing at least one aromatic monomer. The at least one aromatic monomer is preferably a dicarboxylic acid. In the context of this invention, m-phenylenediamine (MXD, CAS No. 1477-55-0) and p-phenylenediamine (PXD, CAS No. 539-48-0) are not aromatic monomers. This also applies to all other monomers in which an amino or carboxyl group is not directly attached to an aromatic ring. The melting temperature and heat of fusion of the partially crystalline, partially aromatic polyamides of this invention can be determined by differential scanning calorimetry (DSC) according to ISO 11357-3 (2013).

[0033] • Metallocene

[0034] Metallocenes are coordination compounds, more specifically, complexes or so-called sandwich complexes. Therefore, they are neither metal oxides nor metal salts.

[0035] One example is unsubstituted or substituted bis(η) 5 (-cyclopentadienyl)iron. Bis(η) 5 2-Cyclopentadienyl iron is also known as ferrocene (CAS No. 102-54-5). These two names are used as synonyms in this application.

[0036] • Heat aging resistance

[0037] Good heat aging resistance is manifested in the slower decrease in tear strength and / or elongation at break after the molded articles are stored at elevated temperatures, i.e., at least 100°C, preferably at least 120°C, more preferably at least 140°C.

[0038] Polyamide molding compound

[0039] The polyamide molding compound according to the invention comprises or consists of components (A), (B), and (C) and optionally (D), wherein component (A) consists of component (A1) and optionally component (A2).

[0040] Polyamide molding compounds contain or consist of the following components:

[0041] (A) 27% to 89.99% by weight of at least one partially crystalline, partially aromatic polyamide (A1) or a mixture of polyamides, said polyamide mixture comprising:

[0042] (A1) At least one partially crystalline, partially aromatic polyamide, and

[0043] (A2) One or more caprolactam-containing polyamides having a caprolactam content of at least 50% by weight and different from the partially crystalline, partially aromatic polyamide (A1).

[0044] The caprolactam content is 5% to 38% by weight relative to the polyamide mixture.

[0045] (B) At least one filler, ranging from 10% to 65% by weight.

[0046] (C) 0.01% to 3.0% by weight of at least one unsubstituted or substituted metallocene,

[0047] (D) At least one additive, ranging from 0% to 35% by weight.

[0048] Components (A) through (D) total 100 by weight.

[0049] The proportion of component (A) in the polyamide molding compound is preferably 35% to 84.87% by weight, more preferably 44.6% to 69.6% by weight, relative to the total weight of the polyamide molding compound.

[0050] The proportion of component (B) in the polyamide molding compound is preferably 15% to 60% by weight, more preferably 30% to 50% by weight, relative to the total weight of the polyamide molding compound.

[0051] The proportion of component (C) in the polyamide molding compound is preferably from 0.03% to 2.0% by weight, more preferably from 0.1% to 1.5% by weight, relative to the total weight of the polyamide molding compound.

[0052] The proportion of component (D) in the molding compound is preferably from 0.1% to 30% by weight, more preferably from 0.3% to 25% by weight, relative to the total weight of the polyamide molding compound.

[0053] The caprolactam content is preferably 5% to 36% by weight, more preferably 10% to 33% by weight, and even more preferably 15% to 30% by weight, relative to the polyamide mixture (A), i.e., relative to the sum of components (A1) and (A2).

[0054] The components of the polyamide molding compound according to the present invention will be described in more detail below.

[0055] Component (A)

[0056] Component (A) consists of component (A1) and optionally component (A2).

[0057] Component (A1)

[0058] According to a preferred embodiment of the present invention, the at least one partially crystalline, partially aromatic polyamide (A1) has:

[0059] • A relative viscosity (RV) of 1.45 to 2.10, preferably 1.50 to 1.90, more preferably 1.55 to 1.80, as measured according to EN ISO 307 (2007), and / or

[0060] • A heat of fusion of at least 25 J / g, preferably at least 30 J / g, more preferably at least 35 J / g, as measured according to EN ISO 11357-3 (2013), and / or

[0061] • A melting temperature of at least 255°C, preferably 270°C to 350°C, and more preferably 280°C to 340°C, as measured according to EN ISO 11357-3 (2013).

[0062] According to a preferred embodiment of the invention, the at least one partially crystalline, partially aromatic polyamide (A1) is formed from monomers (a1.1) to (a1.2) and optionally (a1.3) and optionally (a1.4):

[0063] (a1.1) At least one diamine selected from: 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,12-dodecanediamine, 2-methyl-1,5-pentanediamine, 2-methyl-1,8-octanediamine, bis(4-amino-cyclohexyl)methane, bis(4-amino-3-methyl-cyclohexyl)methane, bis(4-amino-3,5-dimethyl-cyclohexyl)methane, bis(aminomethyl)cyclohexane, isophorone diamine, m-phenylenediamine, and p-phenylenediamine, and

[0064] (a1.2) At least one aromatic dicarboxylic acid selected from: terephthalic acid, isophthalic acid and naphthalic acid, and / or

[0065] (a1.3) At least one dicarboxylic acid selected from: 1,6-adipic acid, 1,9-azelaic acid, 1,10-sebacic acid, 1,12-dodecanoic acid, 1,13-tridecanoic acid, 1,14-tetradecanoic acid, 1,15-pentadecanoic acid, 1,16-hexadecanoic acid, 1,17-heptadecanoic acid, 1,18-octadecanoic acid, cyclohexanedicarboxylic acid, and dimer fatty acids having 36 or 44 carbon atoms, and / or

[0066] (a1.4) One or more lactams or ω-amino acids selected from: lactam-6, lactam-11, lactam-12, 1,6-aminohexanoic acid, 1,11-aminoundecanoic acid and 1,12-aminododecanoic acid.

[0067] According to a more preferred embodiment of the invention, the at least one partially crystalline, partially aromatic polyamide (A1) is formed from monomers (a1.1) to (a1.2) and optionally (a1.3) and optionally (a1.4):

[0068] (a1.1) At least one diamine selected from: 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,12-dodecanediamine, 2-methyl-1,5-pentanediamine, 2-methyl-1,8-octanediamine, bis(4-amino-cyclohexyl)methane, bis(4-amino-3-methyl-cyclohexyl)methane, and bis(aminomethyl)cyclohexane, and

[0069] (a1.2) At least one aromatic dicarboxylic acid, selected from: terephthalic acid and isophthalic acid, and / or

[0070] (a1.3) At least one dicarboxylic acid selected from: 1,6-adipic acid, 1,10-decanedioic acid, 1,12-dodecanoic acid and 1,16-hexadecanoic acid, and / or

[0071] (a1.4) One or more lactams or ω-amino acids selected from: lactam-6, lactam-12, 1,6-aminohexanoic acid and 1,12-aminododecanoic acid.

[0072] According to a more preferred embodiment of the invention, the at least one partially crystalline, partially aromatic polyamide (A1) is formed from monomers (a1.1) to (a1.2) and optionally (a1.3):

[0073] (a1.1) At least one diamine selected from: 1,6-hexanediamine, 1,10-dodecanediamine, and bis(aminomethyl)cyclohexane, and

[0074] (a1.2) At least one aromatic dicarboxylic acid, selected from: terephthalic acid and isophthalic acid, and / or

[0075] (a1.3) At least one dicarboxylic acid selected from: 1,6-adipic acid, 1,10-sebaceous acid and 1,12-dodecanoic acid.

[0076] According to a more preferred embodiment of the present invention, the at least one partially crystalline, partially aromatic polyamide (A1) comprises:

[0077] • At least 10 mol%, preferably at least 20 mol%, more preferably at least 25 mol% of 1,6-hexanediamine, and

[0078] • At least 10 mol%, preferably at least 20 mol%, more preferably at least 25 mol% of terephthalic acid.

[0079] According to another preferred embodiment of the present invention, the at least one partially crystalline, partially aromatic polyamide (A1) is selected from:

[0080] • PA 4T / 66, PA 4T / 6T, PA 4T / 8T, PA 6T / 8T, PA 4T / MPMDT, PA 4T / 6T / MPMDT, PA4T / 4I, PA 4T / 6I, PA 5T / 5I, PA 6T / MPMDT, PA 6T / MPMDT / 6I, PA 6T / 6I, PA 6T / 66, PA 6T / 6, PA 6T / 12, PA 6T / 66 / 6, PA 6T / 610, PA 6T / 612, PA 6T / 10I, PA 6T / 9T, PA 6T / 12T, PA 6T / 6I / 6, PA 6T / 6I / 66, PA 6T / 6I / 612, PA 6T / 6I / 12, PA 9T / MODT, PA 9T / 9I, PA 10T, PA 12T, PA 12T / 12I, PA 10T / 1012, PA 10T / 6T, PA 10T / 10I, PA 10T / 106, PA 10T / 12, PA 10T / 11, PA10T / 6T / 612, PA 10T / 6T / 10I / 6I, PA 10T / 6T / 1012 / 612, PA 6T / BACT, PA 6T / BACT / 66, PA6T / 6I / BACT / BACI, PA 6T / BACT / MACMT, PA 6T / BACT / PACMT, PA 6T / BACT / TMDCT, PA 4T / 6T / 8T, PA 4T / 6T / 10T, PA 4T / 8T / 10T, PA 6T / 8T / 10T and its copolyamide,

[0081] • More preferably selected from PA 6T / MPMDT, PA 6T / 6I, PA 6T / 66, PA 6T / 6, PA 6T / 12, PA 6T / 66 / 6, PA 6T / 6I / 6, PA 6T / 6I / 66, PA 6T / 6I / 612, PA 9T / MODT, PA 10T, PA 12T, PA 10T / 1012, PA10T / 6T, PA 10T / 10I, PA 10T / 6T / 612, PA 10T / 6T / 10I / 6I, PA 10T / 6T / 1012 / 612, PA 6T / BACT, PA 6T / BACT / 66, PA 6T / BACT / MACMT and PA 6T / BACT / PACMT,

[0082] • Even more preferred are PA 6T / 6I, PA 6T / 66, PA 6T / 66 / 6, PA 6T / 6I / 66, PA 6T / 6I / 612, PA 10T / 1012, PA 10T / 6T, PA 10T / 6T / 612, PA 10T / 6T / 10I / 6I, PA 10T / 6T / 1012 / 612, PA 6T / BACT, and PA 6T / BACT / 66.

[0083] According to a more preferred embodiment of the invention, the at least one partially crystalline, partially aromatic polyamide (A1) is free of lactams and ω-amino acids.

[0084] According to a more preferred embodiment of the present invention, the partially crystalline, partially aromatic polyamide (A1) is PA 6T / 66 formed from the following monomers:

[0085] • 50 mol% of 1,6-hexanediamine

[0086] • 14 mol% to 40 mol%, preferably 20 mol% to 35 mol%, more preferably 25 mol% to 30 mol% of terephthalic acid, and

[0087] • 10 mol% to 36 mol%, preferably 15 mol% to 30 mol%, more preferably 20 mol% to 25 mol% of 1,6-adipic acid.

[0088] Component (A2)

[0089] The polyamide (A2) containing caprolactam preferably contains at least 60% by weight, more preferably at least 70% by weight, and even more preferably at least 80% by weight of caprolactam.

[0090] If component (A2) is a copolymer, then, in addition to caprolactam, the preferred comonomers used in (A2) are, on the one hand, a combination of diamine and dicarboxylic acid, which is preferably used in equimolar or nearly equimolar amounts, and on the other hand, a combination of caprolactam and aminocarboxylic acid.

[0091] Suitable diamines are, in particular, branched or straight-chain aliphatic diamines having 4 to 18 carbon atoms. Suitable dicarboxylic acids having 6 to 36 carbon atoms are, in particular, aliphatic, alicyclic, or aromatic dicarboxylic acids.

[0092] According to the preferred embodiment, C4-C 18 The diamine is selected from at least one of the following:

[0093] • 1,4-Butanediamine, 1,5-Pentanediamine, 2-Methylpentanediamine, 1,6-Hexanediamine, 1,7-Heptanediamine, 1,8-Octadecanediamine, 1,9-Nonanediamine, Methyl-1,8-Octadecanediamine, 2,2,4-Trimethylhexanediamine, 2,4,4-Trimethylhexanediamine, 1,10-Decanedanediamine, 1,11-Undecanediamine, 1,12-Dodecanediamine, 1,13-Tetanediamine, 1,14-Tetradecanediamine, 1,15-Pentanediamine, 1,16-Hexadecanediamine, 1,17-Heptadecananediamine, 1,18-Octadecananediamine, bis(4-aminocyclohexyl)methane, 2,2-(4,4'-Diaminodicyclohexyl)propane, bis(4-amino-3-methyl-cyclohexyl)methane, m-phenylenediamine, and p-phenylenediamine.

[0094] • Preferably, 1,6-hexanediamine, 1,10-decanediamine, and 1,12-dodecanediamine are used.

[0095] • More preferably 1,6-hexanediamine and 1,10-decanediamine.

[0096] According to a more preferred embodiment, C4-C 18 The diamine is 1,6-hexanediamine.

[0097] According to the preferred embodiment, C6-C 36 The dicarboxylic acid is selected from at least one of the following:

[0098] • 1,6-Adipic acid, 1,8-Octaic acid, 1,9-Azelaic acid, 1,10-Sebacic acid, 1,11-Undecanoic acid, 1,12-Dodecanoic acid, 1,13-Trigetradecanoic acid, 1,14-Tetradecanoic acid, 1,15-Pentadecanoic acid, 1,16-Hexadecanoic acid, 1,17-Heptadecanoic acid, 1,18-Octadecanoic acid, cyclohexanedicarboxylic acid, dimer fatty acids with 36 or 44 carbon atoms, terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid.

[0099] • Preferably, 1,6-adipic acid, 1,10-decanoic acid, 1,11-undecanoic acid, 1,12-dodecanoic acid, terephthalic acid, and isophthalic acid are used.

[0100] • More preferably 1,6-adipic acid and terephthalic acid.

[0101] According to a more preferred embodiment of the present invention, the dicarboxylic acid is adipic acid.

[0102] More preferred comonomers for polyamide (A2) are lactams or aminocarboxylic acids having 7 to 12 carbon atoms, more preferably lactam-12 and / or 1,12-aminododecanoic acid.

[0103] In a more preferred embodiment of the invention, the at least one caprolactam-containing polyamide (A2) is selected from:

[0104] • PA 6, PA 6 / 12, PA 6 / 6T, PA 6 / 6I, PA 6 / 66, PA 6 / 610, PA 6 / 612, PA 6 / 616, PA6 / 10T, PA 6 / 10I, PA 6 / 106, PA 6 / 1010, PA 6 / 1012, PA 6 / 1016, PA 6 / 611, PA 6 / 1011, PA6 / 126, PA 6 / 12T, PA 6 / 12I, PA 6 / 1210, PA 6 / 1212, PA 6 / 1216, PA 6 / 66 / 69, PA 6 / 66 / 610, PA 6 / 66 / 6T, PA 6 / 66 / 6I, PA 6 / 66 / 612, PA 6 / 66 / 616,PA PA 6 / 6T / 69, PA 6 / 6T / 610, PA 6 / 6T / 6I, PA 6 / 6T / 612, PA 6 / 6T / 616, PA 6 / 6I / 69, PA 6 / 6I / 610, PA 6 / 6I / 612, PA 6 / 6I / 616 and their copolyamides,

[0105] • More preferred are PA 6, PA 6 / 12, PA 6 / 6T, PA 6 / 6I, PA 6 / 66, PA 6 / 610, PA 6 / 612, PA 6 / 616, PA 6 / 10T, PA 6 / 10I, PA 6 / 106, PA 6 / 1010, PA 6 / 1012, PA 6 / 1016, PA 6 / 611, PA 6 / 1011, PA 6 / 126, PA 6 / 12T, PA 6 / 12I, PA 6 / 1210, PA 6 / 1212 and PA 6 / 1216,

[0106] • Even more preferred are PA 6, PA 6 / 12, PA 6 / 6T, PA 6 / 6I, PA 6 / 66, PA 6 / 610, PA 6 / 612, PA6 / 616, PA 6 / 10T and PA 6 / 10I.

[0107] The polyamide containing caprolactam (A2) is even more preferably a partially crystalline aliphatic polyamide.

[0108] The caprolactam-containing polyamide (A2) preferably has a relative viscosity (RV) of 1.6 to 3.0, more preferably 1.7 to 2.5, and very particularly even more preferably 1.8 to 2.2, as measured according to EN ISO 307 (2007).

[0109] Component (B)

[0110] The term "filler" (component (B)) includes fiber fillers, needle fillers, particulate fillers and mixtures thereof.

[0111] Fillers may preferably be coated or surface-treated; that is, they may have a suitable sizing or adhesion promoter system or be otherwise surface-activated. For this purpose, systems based on polyurethane, silane, epoxy resin, polyamide, polyhydroxy ether, acrylate, or combinations or mixtures thereof may be used, for example. The sizing or adhesion promoter system may also include other auxiliary substances such as antistatic agents or lubricants.

[0112] The fibrous or needle-like filler is preferably selected from glass fiber, carbon fiber, basalt fiber, boron fiber, slag fiber, metal fiber, whisker, mineral fiber, wollastonite, aramid fiber, ground glass fiber, ground carbon fiber, ground mineral fiber and mixtures thereof.

[0113] The fibrous or needle-like filler is more preferably selected from glass fiber, carbon fiber, basalt fiber, boron fiber, aramid fiber and mixtures thereof.

[0114] Even more preferably, glass fiber is used exclusively as a fibrous or needle-like filler.

[0115] For glass fiber or carbon fiber, short fibers or continuous filaments (rovings) can be used.

[0116] Glass fibers or carbon fibers have cross-sections that are circular, oval, elliptical, elliptical with a narrowing (so-called cocoon fibers), angular, or rectangular. Fibers with non-circular cross-sections, particularly oval or elliptical fibers, elliptical fibers with one or more narrowing sections (so-called cocoon fibers), and angular or right-angled fibers, are also known as flat fibers. Mixtures of circular and non-circular fibers can also be used.

[0117] Fiberglass can be long or spiral in shape.

[0118] Glass fibers made from all types of glass can be used, such as A-, C-, D-, E-, E-CR-, L-, LD-, M-, NE-, S-, R-, AR-glass, or any mixture thereof. Preferred are glass fibers made from E-glass, S-glass, or mixtures containing E- and / or S-glass fibers.

[0119] The glass short fibers have a fiber length of 1 mm to 50 mm, especially 1 mm to 25 mm, preferably 1.5 mm to 20 mm, more preferably 2 mm to 12 mm, and even more preferably 2 mm to 8 mm.

[0120] Glass fibers, in particular, have a diameter of 5 μm to 20 μm, preferably 5 μm to 15 μm, and more preferably 6 μm to 12 μm.

[0121] If glass fibers are used in continuous filaments (rovings) in the pultrusion process, they preferably have a diameter of no more than 20 μm, more preferably no more than 18 μm, and more preferably 10 μm to 17 μm.

[0122] Carbon fibers, in particular, have a diameter of 3 μm to 12 μm, preferably 4 μm to 10 μm, and more preferably 4 μm to 9 μm.

[0123] In flat fibers, the aspect ratio, i.e., the ratio of the long cross-sectional axis to the short cross-sectional axis, is 1.5 to 8, preferably 2 to 6, more preferably 2.5 to 5, and even more preferably 3 to 4.

[0124] Among flat fibers, flat glass fibers are preferred.

[0125] The cross-sectional axis length of the flat glass fiber is 3µm to 40µm. The length of the short cross-sectional axis is preferably 3µm to 20µm, particularly preferably 4µm to 10µm, and the length of the long cross-sectional axis is 6µm to 40µm, more preferably 12µm to 30µm.

[0126] The particulate filler is preferably selected from dolomite, silicate, quartz, talc, mica, kaolin, perlite, silica, precipitated or fumed silica, diatomaceous earth, titanium dioxide, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, ground or precipitated calcium carbonate, zinc oxide, zinc sulfide, chalk, lime, limestone powder, slate powder, feldspar, barium carbonate, barium sulfate, synthetic silicate, natural silicate, permanent magnet or magnetizable metal or alloy, glass flakes, glass spheres, hollow glass spheres, hollow spherical silicate fillers and mixtures thereof.

[0127] The particulate filler is more preferably selected from silicates, quartz, talc, mica, kaolin, perlite, silica, precipitated or fumed silica, diatomaceous earth, titanium dioxide, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, ground or precipitated calcium carbonate, chalk, lime, limestone powder, slate powder, feldspar, barium carbonate, barium sulfate, synthetic silicates, natural silicates, glass flakes, glass beads, hollow glass beads, hollow silica beads, and mixtures thereof.

[0128] The particulate filler is even more preferably selected from silicates, talc, mica, kaolin, titanium dioxide, ground or precipitated calcium carbonate, chalk, limestone powder, slate powder, synthetic silicates, natural silicates, glass flakes, glass beads, hollow glass beads and mixtures thereof.

[0129] Preferably, at least one fibrous and / or needle-like filler or a mixture of at least one fibrous and / or needle-like filler and at least one particulate filler is used as the filler (component (B)) in the polyamide molding compound according to the invention.

[0130] If a mixture of at least one fibrous and / or needle-like filler with at least one particulate filler is used, the proportion of the particulate filler shall be at most half, preferably at most one-third, and more preferably at most one-quarter of the total filler.

[0131] More preferably, in the polyamide molding compound according to the invention, a mixture of at least one fibrous and / or needle-like filler and at least one particulate filler is used as the filler in a weight ratio of 98:2 to 100:0.

[0132] More preferably, in the polyamide molding compound according to the invention, a mixture of at least one fibrous filler and at least one particulate filler is used as a filler in a weight ratio of 98:2 to 100:0.

[0133] Component (C)

[0134] According to a preferred embodiment, the at least one unsubstituted or substituted metallocene has a melting temperature of 120°C to 350°C, preferably 140°C to 320°C, and more preferably 150°C to 280°C.

[0135] According to a preferred embodiment, the at least one unsubstituted or substituted metallocene has a metal from Groups 3 to 12 or the lanthanides as the central metal atom, preferably vanadium, chromium, manganese, iron, cobalt, nickel, ruthenium, osmium, zinc, rhodium, cadmium, iridium, magnesium, lanthanum, cerium, samarium, zirconium, scandium, yttrium, and combinations thereof, more preferably unsubstituted or substituted bis(n) metallocene. 51,1'-cyclopentadienyl)ferrocene, particularly selected from ferrocene, 3-carboxybutyrylferrocene, 3-carboxypropionylferrocene, 6-mercaptohexylferrocene, aminomethylferrocene, dimethylaminomethylferrocene, diphenylphosphineferrocene, 1-ferrocene acrylonitrile, 1-ferrocene ethanol, 1,1'-bis(1-hydroxyethyl)ferrocene, 1,1'-diacetylferrocene, 1,1'-diaminoferrocene, 1,1'-dibenzoylferrocene, 1,1'-dibutylferrocene, 1,1'-diethylferrocene, 1,1'-dihexylferrocene, 1,1'-dimethylferrocene, 1,1'-divinylferrocene, 1,1'-ferrocene dicarboxaldehyde, 1,1'-ferrocene dicarboxamide, 1,1'-ferrocene dicarboxylic acid, 1,1'-dicyclocene Ferro-2-methylethanol, 1,1'-ferrocene-acetic acid, 1,1'-ferrocene-propionic acid, 1,1'-ferrocene-butyric acid, 1,1'-ferrocene-valeric acid, 1,2,3,4,5-pentamethylferrocene, 2-ferrocene-ethanol, 3-ferrocene-propanol, 3-ferrocene-propionic acid, 4-ferrocene-butyric acid, 5-ferrocene-valeric acid, acetylferrocene, α-(N,N-dimethylamino)ethylferrocene, aminoferrocene, ethylferrocene, ferrocene-acetic acid, ferrocene-methanol, octylferrocene, ferrocene-carboxylic acid, ferrocene-carboxamide, ferrocene-carboxaldehyde, propylferrocene, hexylferrocene, hydroxyethylferrocene, benzoylferrocene, butylferrocene, methylferrocene, vinylferrocene, and bis(pentamethylcyclopentadienyl)ferro(II).

[0136] double (η) 5 2-Cyclopentadienyl iron is also known as ferrocene (CAS No. 102-54-5). These two names are used as synonyms in this application.

[0137] The substituted metallocene can be substituted once or more than once on one or both cyclopentadienyl rings. When both cyclopentadienyl rings are substituted, the substituents can be the same or different, preferably the substituents are the same. Each cyclopentadienyl ring is preferably substituted only once. More preferably, only one of the two cyclopentadienyl rings is substituted. Even more preferably, only one of the two cyclopentadienyl rings is substituted once.

[0138] The substituents are preferably selected from alkyl, alkylene and aryl groups, carboxylic acid groups, carboxylic acid derivative groups, oxoalkyl acid groups, alcohol groups, amine groups and phosphorus-containing substituents.

[0139] The substituents are preferably selected from alkyl groups having 1 to 12 carbon atoms, alkylene groups having 2 to 12 carbon atoms, aryl groups having 6 to 12 carbon atoms, carboxylic acid groups having 1 to 12 carbon atoms, carboxylic acid ester groups having 2 to 20 carbon atoms, carboxylic acid anhydride groups having 2 to 12 carbon atoms, oxoalkanoic acid groups having 1 to 12 carbon atoms, alcohol groups having 1 to 12 carbon atoms, amine groups having 0 to 12 carbon atoms, and phosphorus-containing substituents.

[0140] The substituents are more preferably selected from alkyl groups having 1 to 9 carbon atoms, alkylene groups having 2 to 9 carbon atoms, aryl groups having 6 to 9 carbon atoms, carboxylic acid groups having 1 to 9 carbon atoms, carboxylic acid ester groups having 2 to 18 carbon atoms, carboxylic acid anhydride groups having 2 to 9 carbon atoms, oxoalkyl acid groups having 1 to 9 carbon atoms, alcohol groups having 1 to 9 carbon atoms, amine groups having 0 to 9 carbon atoms, and phosphorus-containing substituents.

[0141] The substituents are even more preferably selected from alkyl groups having 1 to 6 carbon atoms, alkylene groups having 2 to 6 carbon atoms, aryl groups having 6 to 7 carbon atoms, carboxylic acid groups having 1 to 6 carbon atoms, carboxylic acid ester groups having 2 to 14 carbon atoms, carboxylic acid anhydride groups having 2 to 6 carbon atoms, oxoalkanoic acid groups having 1 to 6 carbon atoms, alcohol groups having 1 to 6 carbon atoms, amine groups having 0 to 6 carbon atoms, and phosphorus-containing substituents.

[0142] According to a preferred embodiment of the present invention, the at least one unsubstituted or substituted metallocene bis(n) 51,1'-Cyclopentadienyl ferrocene is selected from ferrocene, 3-carboxybutyryl ferrocene, 3-carboxypropionyl ferrocene, 6-mercaptohexyl ferrocene, aminomethyl ferrocene, dimethylaminomethyl ferrocene, diphenylphosphine ferrocene, 1-ferrocene acrylonitrile, 1-ferrocene ethanol, 1,1'-bis(1-hydroxyethyl)ferrocene, 1,1'-diacetylferrocene, 1,1'-diaminoferrocene, 1,1'-dibenzoylferrocene, 1,1'-dibutylferrocene, 1,1'-diethylferrocene, 1,1'-dihexylferrocene, 1,1'-dimethylferrocene, 1,1'-divinylferrocene, 1,1'-ferrocene dicarboxaldehyde, 1,1'-ferrocene dicarboxamide, 1,1'-ferrocene dicarboxylic acid, 1,1'-ferrocene dicarboxylic acid, etc. Methanol, 1,1'-ferrocene acetic acid, 1,1'-ferrocene propionic acid, 1,1'-ferrocene butyric acid, 1,1'-ferrocene valerate, 1,2,3,4,5-pentamethylferrocene, 2-ferrocene ethanol, 3-ferrocene propanol, 3-ferrocene propionic acid, 4-ferrocene butyric acid, 5-ferrocene valerate, acetylferrocene, α-(N,N-dimethylamino)ethylferrocene, aminoferrocene, ethylferrocene, ferrocene acetic acid, ferrocene methanol, octylferrocene, ferrocene carboxylic acid, ferrocene carboxamide, ferrocene carboxaldehyde, propylferrocene, hexylferrocene, hydroxyethylferrocene, benzoylferrocene, butylferrocene, methylferrocene, vinylferrocene, and bis(pentamethylcyclopentadienyl)ferro(II).

[0143] According to a more preferred embodiment of the invention, the at least one unsubstituted or substituted metallocene bis(n) 5 1,1'-Cyclopentadienyl iron is selected from ferrocene, aminoferrocene, 1,1'-diaminoferrocene, ferrocene carboxylic acid, 1,1'-ferrocene dicarboxylic acid, aminomethylferrocene, 1,1'-bis(aminomethyl)ferrocene, dimethylaminomethylferrocene, 1,1'-bis(dimethylaminomethyl)ferrocene, ferrocene acetic acid, 1,1'-ferrocene acetic acid, ferrocene methanol, 1,1'-ferrocene dimethanol, ferrocene formaldehyde, 1,1'-ferrocene dicarboxaldehyde, acetylferrocene, 1,1'-diacetylferrocene, methylferrocene, and 1,1'-dimethylferrocene.

[0144] According to a more preferred embodiment of the invention, the at least one unsubstituted or substituted metallocene bis(n) 5 1,1'-Cyclopentadienyl)iron is selected from ferrocene, aminoferrocene, 1,1'-diaminoferrocene, ferrocene carboxylic acid, 1,1'-ferrocene dicarboxylic acid, aminomethylferrocene, 1,1'-bis(aminomethyl)ferrocene, ferrocene acetic acid and 1,1'-ferrocene acetic acid.

[0145] According to an even more preferred embodiment of the invention, the at least one unsubstituted or substituted metallocene bis(n) 5 -Cyclopentadienyl) iron is ferrocene.

[0146] Component (D)

[0147] According to a preferred embodiment of the present invention, the at least one additive (component (D)) is different from component (C) and is selected from inorganic stabilizers, organic stabilizers, especially antioxidants, anti-ozone agents, light stabilizers, UV stabilizers, UV absorbers or UV blockers, IR absorbers, NIR absorbers, anti-blocking agents, nucleating agents, crystallization promoters, crystallization delayers, chain extenders, conductive additives, separating agents, lubricants, dyes, markers, inorganic pigments, organic pigments, carbon black, graphite, carbon nanotubes, graphene, titanium dioxide, zinc sulfide, zinc oxide, barium carbonate, barium sulfate, photochromic agents, antistatic agents, release agents, fluorescent whitening agents, halogen-free flame retardants, metallic pigments, metallic flakes, metallic coated particles, and mixtures thereof.

[0148] In a more preferred embodiment of the present invention, the at least one additive (component (D)) is selected from organic stabilizers, particularly antioxidants, anti-ozone agents, light stabilizers, UV stabilizers, UV absorbers or UV blockers, IR absorbers, NIR absorbers, anti-blocking agents, nucleating agents, crystallization promoters, crystallization delayers, chain extenders, conductive additives, separating agents, lubricants, dyes, markers, inorganic pigments, organic pigments, carbon black, graphite, carbon nanotubes, graphene, photochromic agents, antistatic agents, release agents, fluorescent whitening agents, halogen-free flame retardants, metallic pigments, metallic flakes, metallic coated particles, and mixtures thereof.

[0149] Among organic stabilizers, phenolic compounds, phosphite compounds, phosphonite compounds, hindered amine-based stabilizers (HALS), or mixtures thereof are preferred.

[0150] The at least one additive may also be added in the form of a masterbatch. Polyamide or polyolefin is preferably used as the base polymer. The polyamide is preferably selected from PA 6, PA 66, PA 6 / 12, PA 6 / 66, PA 6 / 69, PA 12, PA 1012, PA 1212 and mixtures thereof, or composed of polyamide (A1) or (A2) or a mixture of polyamides (A).

[0151] Molded products

[0152] According to the invention, molded articles that can be produced from or include the previously described molding compounds are also provided. The molded articles according to the invention can be produced from the polyamide molding compounds according to the invention using conventional processing techniques such as injection molding, extrusion, or blow molding, particularly by injection molding. These molded articles are preferably molded articles used in the automotive field, particularly engine compartments, or in the fields of electrical engineering, electronics, mechanical engineering, energy production, and energy supply.

[0153] The preferred embodiment specifies that the molded parts are selected from cylinder head covers, engine covers, housings and parts for intercoolers, intercooler valves, intake pipes, especially intake manifolds, exhaust lines, connectors, gears, fan impellers, coolant tanks, housings or parts for heat exchangers, coolant coolers, thermostats, water pumps, heating elements, fasteners, printed circuit boards, membranes, wiring, housings and parts for electrical / electronic equipment, housings and parts for hot air fans, switches, distributors, relays, resistors, capacitors, coils, lamps, diodes, LEDs, transistors, connectors, controllers, storage devices, and sensors.

[0154] use

[0155] The present invention also relates to the use of the polyamide molding compound as defined above according to the invention in the production of components for use in the automotive field, particularly in engine compartments, or in the fields of electrical engineering, electronics, mechanical engineering, energy production, and energy supply, such components as cylinder head covers, engine covers, housings and parts for intercoolers, intercooler valves, intake pipes, particularly intake manifolds, exhaust lines, connectors, gears, fan impellers, coolant tanks, housings or parts for heat exchangers, coolant coolers, thermostats, water pumps, heating elements, fasteners, printed circuit boards, membranes, wiring, housings and parts for electrical / electronic equipment, housings and parts for hot air fans, switches, distributors, relays, resistors, capacitors, coils, lamps, diodes, LEDs, transistors, connectors, controllers, storage devices, and sensors.

[0156] The measurement methods, storage conditions, and production of the samples

[0157] Relative viscosity:

[0158] The relative viscosity was determined at 20°C according to ISO 307 (2007). For this purpose, 0.5 g of polymer particles were weighed into 100 ml of m-cresol and the relative viscosity (RV) was calculated based on Section 11 of the standard according to RV = t / t0.

[0159] Melting temperature and heat of fusion:

[0160] The determination of granular materials was performed according to ISO 11357-3 (2013).

[0161] Differential scanning calorimetry (DSC) was performed on each of the two heating processes at a heating rate of 20 K / min. After the first heating, cooling was carried out at a rate of 20 K / min. The melting temperature and heat of fusion were measured during the second heating. The temperature at which the maximum peak value was designated as the melting temperature.

[0162] Tear strength and elongation at break:

[0163] The test was conducted according to ISO 527 at a tension rate of 5 mm / min and a temperature of 23°C. ISO tension bars (Type A1, dimensions 170 × 20 / 10 × 4) manufactured according to standard ISO / CD 3167 (2003), and stored at elevated temperatures and then further stored, were used as specimens. For cooling, the ISO tension bars were stored at room temperature in a dry environment, i.e., on silica gel, for at least 48 hours prior to the tension test.

[0164] Storage conditions:

[0165] Store in a drying oven at 180°C, 200°C, and 220°C.

[0166] For all storage, sampling was performed at the same time, specifically after 504 hours, 1008 hours, 1512 hours, and 2016 hours. For each material storage time and storage temperature, five ISO pull rods (Type A1, dimensions 170 × 20 / 10 × 4, manufactured according to standard ISO / CD 3167 (2003)) were stored, and the arithmetic mean of the five measurements was formed.

[0167] Helical flow test:

[0168] A flow spiral was generated on an Allrounder 420 C 100-250 injection molding machine from Arburg at a material temperature of 330°C and a mold temperature of 80°C using an injection pressure of 1000 bar.

[0169] The flow spiral has a centrally located gate with a cross-section of 1.5 × 10 mm. The spiral includes the following removal markings:

[0170] • Points at a distance of 1mm

[0171] • Stripes at whole centimeters

[0172] • Length specifications per 5cm

[0173] Sample production:

[0174] To produce ISO tie rods, granular materials with a moisture content of less than 0.1% by weight are used.

[0175] The ISO tie rods are manufactured on an injection molding machine from Arburg, specifically the Allrounder 420 C1000-250. This utilizes a cylinder temperature that rises and falls from the feed nozzle.

[0176] Cylinder temperature: 310℃ to 340℃

[0177] Mold temperature: 120℃

[0178] Unless otherwise specified, use the samples in a dry condition; for this purpose, store them at room temperature in a dry environment, i.e., on silicone, for at least 48 hours after injection molding.

[0179] General Production Instructions for Polyamide Molding Compounds According to the Invention

[0180] To produce the polyamide molding compound according to the invention, components (A1), (B), (C), and optionally (A2) and optionally (D) are mixed in a conventional compounding machine such as a single-shaft or twin-shaft extruder or a screw compounder. In this case, the components are individually metered into the feed or into a side feeder via a gravimetric or volumetric weighing scale or supplied as a dry mix.

[0181] If additives (component (D)) are used, they can be introduced directly or in the form of a masterbatch. The carrier material of the masterbatch is preferably polyamide or polyolefin. The polyamide is preferably selected from PA 6, PA 66, PA 6 / 12, PA 6 / 66, PA 6 / 69, PA12, PA 1012, PA 1212 and mixtures thereof, or consists of polyamide (A1) or (A2) or a mixture of polyamides (A).

[0182] To produce a dry mix, the dry granular materials of polyamide (A1), component (C), and optionally polyamide (A2) and optional additive (D) are mixed in a closed container. The mixture is homogenized for 10 to 40 minutes using a drum mixer, ring drum mixer, or drum dryer. To avoid moisture absorption, mixing can be carried out under a dry, inert gas atmosphere.

[0183] Compounding is carried out at a series of cylinder temperatures ranging from 300°C to 380°C, with the temperature of the first cylinder set from 50°C to 100°C. Degassing can be performed before the nozzle. This can be done under vacuum or atmospheric pressure. The melt is discharged in the form of thin strips, cooled in a water bath at 10°C to 80°C, and then granulated. Alternatively, the melt can be forced into a water bath through a perforated plate with a cutting device, and the cut granules can be separated in a post-processing section (underwater granulation). The granules are dried at up to 100°C under nitrogen or vacuum until the moisture content is less than 0.1% by weight.

[0184] The subject matter of the invention will be described in more detail based on the following embodiments, but it is not intended to limit it to the specific implementations shown herein.

[0185] Examples and Comparative Examples

[0186] Starting materials

[0187] The materials used in the examples and comparative examples are summarized in Table 1.

[0188] Table 1: Materials used in the examples and comparative examples

[0189]

[0190] RV: Relative viscosity, measured at 20°C using a solution of 0.5 g polyamide in 100 ml m-cresol.

[0191] Production of polyamide molding compound according to Example 2

[0192] The dry granular materials of polyamides (A1.1) and (A2), filler (B2), ferrocene (C), and additive (D1) are precisely mixed into a dry mix at the ratios specified in Table 2. The mixture is homogenized using a drum mixer for approximately 20 minutes.

[0193] Polyamide molding compounds were produced on a ZSK 25 twin-screw extruder from Werner & Pfleiderer. The dry mix was metered into the feed using a metering scale. Glass fiber (B1) was fed into the melt using the metering scale and the six housing zones of the side feeder before the nozzle.

[0194] The temperature of the first shell is set to 50°C, and the temperatures of the remaining shells are set to 305 to 330°C. A rotational speed of 150 rpm and a throughput of 15 kg / h are used. Degassing is not performed. The melt strips are cooled in a water bath, cut, and the resulting granular material is dried under vacuum (30 mbar) at 100°C for 24 hours until the moisture content is less than 0.1% by weight.

[0195] The results of the embodiments and comparative examples according to the present invention are summarized in Tables 2 to 4 below.

[0196] Table 2: Tests without PA 6, tear strength expressed in MPa and % relative to initial value.

[0197]

[0198] Table 3: Tests with PA 6, elongation at break (%)

[0199]

[0200] Table 4: Tests without PA 6, tear strength expressed in MPa and % relative to the initial value.

[0201]

[0202] Table 5: Tests without PA 6, elongation at break (in %)

[0203]

[0204] Table 6 shows the results of the spiral flow test on the polyamide molding compounds of Example 1 and Comparative Example 3.

[0205] Table 6: Spiral flow test for determining the flow length (flowability) of polyamide molding compounds of Example 1 and Comparative Example 3.

[0206]

[0207] Results Discussion

[0208] The results in Tables 2 and 3 show that, after storage, the polyamide molding compounds produced from polyamide molding compounds, compared with the polyamide molding compounds containing polyamide 6 from components (D2) and (D3) of Comparative Examples 3 and 5, more specifically at all three storage temperatures (180°C, 200°C, and 220°C) and storage times from 504 hours to 3024 hours, exhibit both improved tear strength and improved elongation at break of the polyamide molding compounds containing ferrocene (C) as a stabilizer according to Examples 1, 2, and 4 of the present invention.

[0209] The results in Tables 3 and 4 show that, after storage, the polyamide molding compounds produced from polyamide molding compounds, compared with the polyamide molding compounds of Comparative Examples 7 and 9 containing inorganic stabilizers from components (D2) and (D3) that do not contain polyamide 6, more specifically at all three storage temperatures (180°C, 200°C, and 220°C) and storage times from 504 hours to 2016 hours, exhibit both improved tear strength and improved elongation at break of the polyamide molding compounds of Examples 6 and 8 of the present invention that contain ferrocene (C) as a stabilizer.

[0210] The results in Table 6 show that, compared with the polyamide molding compounds of Comparative Examples 3 and 7 containing inorganic stabilizers from components (D2) and (D3), the polyamide molding compounds of Examples 1 and 6 of the present invention containing ferrocene (C) as a stabilizer have significantly improved flowability.

Claims

1. A polyamide molding compound, wherein the polyamide molding compound comprises or consists of: (A) 27% to 89.99% by weight of at least one partially crystalline, partially aromatic polyamide (A1) or a mixture of polyamides, said polyamide mixture comprising: (A1) At least one partially crystalline, partially aromatic polyamide, and (A2) At least one caprolactam-containing polyamide having a caprolactam content of at least 50% by weight and different from the partially crystalline, partially aromatic polyamide (A1). The caprolactam content is from 5% to 38% by weight relative to the polyamide mixture. (B) At least one filler, ranging from 10% to 65% by weight. (C) 0.01 wt% to 3.0 wt% of at least one unsubstituted or substituted metallocene, wherein the at least one unsubstituted or substituted metallocene has iron as a central metal atom. (D) At least one additive, ranging from 0% to 35% by weight. Components (A) through (D) total 100 by weight.

2. The polyamide molding compound according to claim 1, characterized in that... The at least one partially crystalline, partially aromatic polyamide (Al) has at least one of the following properties: • The relative viscosity (RV) measured according to EN ISO 307 (2007) is 1.45 to 2.

10. • The heat of fusion, as measured according to EN ISO 11357-3 (2013), is at least 25 J / g. • The melting temperature, as determined by EN ISO 11357-3 (2013), is at least 255°C.

3. The polyamide molding compound according to claim 2, characterized in that... The relative viscosity (RV) measured according to EN ISO 307 (2007) is 1.50 to 1.

90.

4. The polyamide molding compound according to claim 3, characterized in that... The relative viscosity (RV) measured according to EN ISO 307 (2007) is 1.55 to 1.

80.

5. The polyamide molding compound according to claim 2, characterized in that... The heat of fusion, as measured according to EN ISO 11357-3 (2013), is at least 30 J / g.

6. The polyamide molding compound according to claim 5, characterized in that... The heat of fusion, as measured according to EN ISO 11357-3 (2013), is at least 35 J / g.

7. The polyamide molding compound according to claim 2, characterized in that... The melting temperature, as determined by EN ISO 11357-3 (2013), is 270°C to 350°C.

8. The polyamide molding compound according to claim 7, characterized in that... The melting temperature, as measured by EN ISO 11357-3 (2013), is 280°C to 340°C.

9. The polyamide molding compound according to claim 1 or 2, characterized in that... The at least one partially crystalline, partially aromatic polyamide (A1) is formed from monomers (a1.1) to (a1.2) and optionally (a1.3) and optionally (a1.4): (a1.1) At least one diamine selected from: 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,12-dodecanediamine, 2-methyl-1,5-pentanediamine, 2-methyl-1,8-octanediamine, bis(4-amino-cyclohexyl)methane, bis(4-amino-3-methyl-cyclohexyl)methane, bis(4-amino-3,5-dimethyl-cyclohexyl)methane, bis(aminomethyl)cyclohexane, isophorone diamine, m-phenylenediamine, and p-phenylenediamine, and (a1.2) At least one aromatic dicarboxylic acid selected from: terephthalic acid, isophthalic acid and naphthalic acid, and / or (a1.3) At least one dicarboxylic acid selected from: 1,6-adipic acid, 1,9-azelaic acid, 1,10-sebacic acid, 1,12-dodecanoic acid, 1,13-tridecanoic acid, 1,14-tetradecanoic acid, 1,15-pentadecanoic acid, 1,16-hexadecanoic acid, 1,17-heptadecanoic acid, 1,18-octadecanoic acid, cyclohexanedicarboxylic acid, and dimer fatty acids having 36 or 44 carbon atoms, and / or (a1.4) One or more lactams or ω-amino acids selected from: lactam-6, lactam-11, lactam-12, 1,6-aminohexanoic acid, 1,11-aminoundecanoic acid and 1,12-aminododecanoic acid.

10. The polyamide molding compound according to claim 1 or 2, characterized in that... The at least one partially crystalline, partially aromatic polyamide (A1) is selected from: • PA 4T / 66, PA 4T / 6T, PA 4T / 8T, PA 6T / 8T, PA 4T / MPMDT, PA 4T / 6T / MPMDT, PA 4T / 4I, PA 4T / 6I, PA 5T / 5I, PA 6T / MPMDT, PA 6T / MPMDT / 6I, PA 6T / 6I, PA 6T / 66, PA 6T / 6, PA6T / 12, PA 6T / 66 / 6, PA 6T / 610, PA 6T / 612, PA 6T / 10I, PA 6T / 9T, PA 6T / 12T, PA 6T / 6I / 6, PA 6T / 6I / 66, PA 6T / 6I / 612, PA 6T / 6I / 12, PA 9T / MODT, PA 9T / 9I, PA 10T, PA 12T, PA12T / 12I, PA 10T / 1012, PA 10T / 6T, PA 10T / 10I, PA10T / 106, PA10T / 12, PA10T / 11, PA 10T / 6T / 612, PA 10T / 6T / 10I / 6I, PA 10T / 6T / 1012 / 612, PA 6T / BACT, PA 6T / BACT / 66, PA 6T / 6I / BACT / BACI, PA 6T / BACT / MACMT, PA 6T / BACT / PACMT, PA 6T / BACT / TMDCT, PA 4T / 6T / 8T, PA4T / 6T / 10T, PA 4T / 8T / 10T and PA 6T / 8T / 10T.

11. The polyamide molding compound according to claim 1 or 2, characterized in that... The at least one partially crystalline, partially aromatic polyamide (A1) is selected from: PA 6T / MPMDT, PA 6T / 6I, PA 6T / 66, PA 6T / 6, PA 6T / 12, PA 6T / 66 / 6, PA 6T / 6I / 6, PA6T / 6I / 66, PA 6T / 6I / 612, PA 9T / MODT, PA 10T, PA 12T, PA 10T / 1012, PA 10T / 6T, PA 10T / 10I, PA 10T / 6T / 612, PA 10T / 6T / 10I / 6I, PA 10T / 6T / 1012 / 612, PA 6T / BACT, PA 6T / BACT / 66, PA 6T / BACT / MACMT and PA 6T / BACT / PACMT.

12. The polyamide molding compound according to claim 1 or 2, characterized in that... The at least one partially crystalline, partially aromatic polyamide (A1) is selected from: PA 6T / 6I, PA 6T / 66, PA 6T / 66 / 6, PA 6T / 6I / 66, PA 6T / 6I / 612, PA 10T / 1012, PA 10T / 6T, PA 10T / 6T / 612, PA 10T / 6T / 10I / 6I, PA 10T / 6T / 1012 / 612, PA 6T / BACT and PA 6T / BACT / 66.

13. The polyamide molding compound according to claim 1 or 2, characterized in that... The at least one partially crystalline, partially aromatic polyamide (A1) is free of lactams and ω-amino acids.

14. The polyamide molding compound according to claim 1 or 2, characterized in that... The partially crystalline, partially aromatic polyamide (A1) is PA 6T / 66 formed from the following monomers: • 50 mol% of 1,6-hexanediamine • 14 mol% to 40 mol% terephthalic acid, and • 10 mol% to 36 mol% of 1,6-adipic acid.

15. The polyamide molding compound according to claim 14, characterized in that... The amount of terephthalic acid is 20 mol% to 35 mol%.

16. The polyamide molding compound according to claim 15, characterized in that... The amount of terephthalic acid is 25 mol% to 30 mol%.

17. The polyamide molding compound according to claim 14, characterized in that... The amount of the 1,6-adipic acid is from 15 mol% to 30 mol%.

18. The polyamide molding compound according to claim 17, characterized in that... The amount of the 1,6-adipic acid is 20 mol% to 25 mol%.

19. The polyamide molding compound according to claim 1 or 2, characterized in that... The at least one caprolactam-containing polyamide (A2) comprises or consists of at least 60% by weight of caprolactam.

20. The polyamide molding compound according to claim 19, characterized in that... The at least one caprolactam-containing polyamide (A2) comprises or consists of at least 70% by weight of caprolactam.

21. The polyamide molding compound according to claim 20, characterized in that... The at least one caprolactam-containing polyamide (A2) comprises or consists of at least 80% by weight caprolactam.

22. The polyamide molding compound according to claim 1 or 2, characterized in that... The at least one caprolactam-containing polyamide (A2) is selected from: • PA 6, PA 6 / 12, PA 6 / 6T, PA 6 / 6I, PA 6 / 66, PA 6 / 610, PA 6 / 612, PA 6 / 616, PA 6 / 10T, PA 6 / 10I, PA 6 / 106, PA 6 / 1010, PA 6 / 1012, PA 6 / 1016, PA 6 / 611, PA 6 / 1011, PA 6 / 126, PA 6 / 12T, PA 6 / 12I, PA 6 / 1210, PA 6 / 1212, PA 6 / 1216, PA 6 / 66 / 69, PA 6 / 66 / 610, PA6 / 66 / 6T, PA 6 / 66 / 6I, PA 6 / 66 / 612, PA 6 / 66 / 616,PA 6 / 6T / 69, PA 6 / 6T / 610, PA 6 / 6T / 6I, PA 6 / 6T / 612, PA 6 / 6T / 616, PA 6 / 6I / 69, PA 6 / 6I / 610, PA 6 / 6I / 612 and PA 6 / 6I / 616.

23. The polyamide molding compound according to claim 1 or 2, characterized in that... The at least one caprolactam-containing polyamide (A2) is selected from: PA 6, PA 6 / 12, PA 6 / 6T, PA 6 / 6I, PA 6 / 66, PA 6 / 610, PA 6 / 612, PA 6 / 616, PA 6 / 10T, PA 6 / 10I, PA 6 / 106, PA 6 / 1010, PA 6 / 1012, PA 6 / 1016, PA 6 / 611, PA 6 / 1011, PA 6 / 126, PA 6 / 12T, PA 6 / 12I, PA 6 / 1210, PA 6 / 1212 and PA 6 / 1216.

24. The polyamide molding compound according to claim 1 or 2, characterized in that... The at least one caprolactam-containing polyamide (A2) is selected from: PA 6, PA 6 / 12, PA 6 / 6T, PA 6 / 6I, PA 6 / 66, PA 6 / 610, PA 6 / 612, PA 6 / 616, PA 6 / 10T and PA 6 / 10I.

25. The polyamide molding compound according to claim 1 or 2, characterized in that... The relative viscosity (RV) of the at least one caprolactam-containing polyamide (A2) as measured according to EN ISO 307 (2007) is from 1.6 to 3.

0.

26. The polyamide molding compound according to claim 25, characterized in that... The relative viscosity of the at least one caprolactam-containing polyamide (A2) is from 1.7 to 2.5, as measured according to EN ISO 307 (2007).

27. The polyamide molding compound according to claim 26, characterized in that... The relative viscosity of the at least one caprolactam-containing polyamide (A2) is from 1.8 to 2.2, as measured according to EN ISO 307 (2007).

28. The polyamide molding compound according to claim 1 or 2, characterized in that... The at least one filler is selected from: • Fibrous or needle-like fillers, • Particulate fillers, and • Its mixture.

29. The polyamide molding compound according to claim 28, characterized in that... The fibrous or needle-like filler is selected from glass fiber, carbon fiber, basalt fiber, boron fiber, slag fiber, metal fiber, whisker, mineral fiber, wollastonite, aramid fiber, ground glass fiber, ground carbon fiber, ground mineral fiber, and mixtures thereof.

30. The polyamide molding compound according to claim 29, characterized in that... The fibrous or needle-like filler is selected from glass fiber, carbon fiber, basalt fiber, boron fiber, aramid fiber and mixtures thereof.

31. The polyamide molding compound according to claim 30, characterized in that... The fibrous or needle-like filler is glass fiber.

32. The polyamide molding compound according to claim 28, characterized in that... The particulate filler is selected from dolomite, silicate, quartz, talc, mica, kaolin, perlite, silicon dioxide, diatomite, titanium dioxide, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, ground or precipitated calcium carbonate, zinc oxide, zinc sulfide, chalk, lime, limestone powder, slate powder, feldspar, barium carbonate, barium sulfate, permanent magnet or magnetizable metal or alloy, glass flakes, glass spheres and mixtures thereof.

33. The polyamide molding compound according to claim 32, characterized in that... The particulate filler is selected from silicates, talc, mica, kaolin, titanium dioxide, ground or precipitated calcium carbonate, chalk, limestone powder, slate powder, glass flakes, glass beads and mixtures thereof.

34. The polyamide molding compound according to claim 32, characterized in that... The silica is precipitated or fumed silica.

35. The polyamide molding compound according to claim 32, characterized in that... The silicate is synthetic foliated silicate, natural foliated silicate, or hollow spherical silicate filler.

36. The polyamide molding compound according to claim 32, characterized in that... The glass sphere is a hollow glass sphere.

37. The polyamide molding compound according to claim 1 or 2, characterized in that... The at least one unsubstituted or substituted metallocene has a melting temperature of 120°C to 350°C.

38. The polyamide molding compound according to claim 37, characterized in that... The at least one unsubstituted or substituted metallocene has a melting temperature of 140°C to 320°C.

39. The polyamide molding compound according to claim 38, characterized in that... The at least one unsubstituted or substituted metallocene has a melting temperature of 150°C to 280°C.

40. The polyamide molding compound according to claim 1 or 2, characterized in that... The at least one unsubstituted or substituted metallocene is an unsubstituted or substituted bis(η) 5 -cyclopentadienyl)iron.

41. The polyamide molding compound according to claim 1 or 2, characterized in that... The unsubstituted or substituted metallocene is selected from ferrocene, 3-carboxybutyrylferrocene, 3-carboxypropionylferrocene, 6-mercaptohexylferrocene, aminomethylferrocene, dimethylaminomethylferrocene, diphenylphosphineferrocene, 1-ferrocene acrylonitrile, 1-ferrocene ethanol, 1,1'-bis(1-hydroxyethyl)ferrocene, 1,1'-diacetylferrocene, 1,1'-diaminoferrocene, 1,1'-dibenzoylferrocene, 1,1'-dibutylferrocene, 1,1'-diethylferrocene, 1,1'-dihexylferrocene, 1,1'-dimethylferrocene, 1,1'-divinylferrocene, 1,1'-ferrocene dicarboxaldehyde, 1,1'-ferrocene dicarboxamide, 1,1'-ferrocene dicarboxylic acid, 1,1'-ferrocene Ferro-2-methylethanol, 1,1'-ferrocene-acetic acid, 1,1'-ferrocene-propionic acid, 1,1'-ferrocene-butyric acid, 1,1'-ferrocene-valeric acid, 1,2,3,4,5-pentamethylferrocene, 2-ferrocene-ethanol, 3-ferrocene-propanol, 3-ferrocene-propionic acid, 4-ferrocene-butyric acid, 5-ferrocene-valeric acid, acetylferrocene, α-(N,N-dimethylamino)ethylferrocene, aminoferrocene, ethylferrocene, ferrocene-acetic acid, ferrocene-methanol, octylferrocene, ferrocene-carboxylic acid, ferrocene-carboxamide, ferrocene-carboxaldehyde, propylferrocene, hexylferrocene, hydroxyethylferrocene, benzoylferrocene, butylferrocene, methylferrocene, vinylferrocene, and bis(pentamethylcyclopentadienyl)ferro(II).

42. The polyamide molding compound according to claim 1 or 2, characterized in that... The at least one additive is different from component (C) and is selected from inorganic stabilizers, organic stabilizers, UV absorbers or UV blockers, IR absorbers, NIR absorbers, anti-blocking agents, nucleating agents, crystallization promoters, crystallization delayers, chain extenders, conductive additives, separating agents, lubricants, dyes, markers, inorganic pigments, organic pigments, carbon black, graphite, carbon nanotubes, graphene, titanium dioxide, zinc sulfide, zinc oxide, barium carbonate, barium sulfate, photochromic agents, antistatic agents, release agents, fluorescent whitening agents, halogen-free flame retardants, metallic pigments, metallic flakes, metallic coated particles, and mixtures thereof.

43. The polyamide molding compound according to claim 42, characterized in that... The inorganic or organic stabilizer is an antioxidant, an ozone desiccant, a light stabilizer, or a UV stabilizer.

44. The polyamide molding compound according to claim 1 or 2, characterized in that... The polyamide molding compound comprises or consists of 35% to 84.87% by weight of component (A), 15% to 60% by weight of component (B), 0.03% to 2.0% by weight of component (C), and 0.1% to 30% by weight of component (D).

45. The polyamide molding compound according to claim 44, characterized in that... The polyamide molding compound comprises or consists of 44.6% to 69.6% by weight of component (A), 30% to 50% by weight of component (B), 0.1% to 1.5% by weight of component (C), and 0.3% to 25% by weight of component (D).

46. ​​A molding article capable of being produced from a polyamide molding compound according to any one of claims 1 to 45.

47. The molded article according to claim 46, characterized in that... The molded parts are components used in the automotive, electrical engineering, electronics, mechanical engineering, energy production, and energy supply fields.

48. The molded article according to claim 46, characterized in that... The molded part is a component in the engine compartment.

49. The molded article according to claim 46, characterized in that... The molded parts are cylinder head covers, engine covers, housings for intercoolers, intercooler valves, intake pipes, exhaust pipes, connectors, gears, fan impellers, coolant tanks, heat exchanger housings, coolant coolers, thermostats, water pumps, heating elements, fasteners, printed circuit boards, membranes, wiring, hot air fan housings, switches, distributors, relays, resistors, capacitors, coils, lamps, transistors, connectors, controllers, storage devices, and sensor components.

50. The molded article according to claim 46, characterized in that... The molded parts are intake manifolds, housings of electrical / electronic devices, and components of diodes and LEDs.

51. Use of the polyamide molding compound according to any one of claims 1 to 45 in the production of components for the automotive industry, or for the electrical engineering, electronics, mechanical engineering, energy production and energy supply industries.

52. The use according to claim 51, characterized in that... The components mentioned in the automotive field are those located in the engine compartment.

53. The use according to claim 51, characterized in that... The components include cylinder head cover, engine cover, housing for intercooler, intercooler valve, intake manifold, exhaust manifold, connector, gear, fan impeller, coolant tank, heat exchanger housing, coolant cooler, thermostat, water pump, heating element, fastener, printed circuit board, membrane, wiring, hot fan housing, switch, distributor, relay, resistor, capacitor, coil, lamp, transistor, connector, controller, storage device, and sensor.

54. The use according to claim 51, characterized in that... The components are the intake manifold, the housing of electrical / electronic equipment, diodes, and LEDs.

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