Polyamide moulding compositions with improved thermal aging resistance

Abstract

The present disclosure describes a thermoplastic molding composition that can include from about 30% to about 99.9% by weight of at least one thermoplastic polyamide as component A; from about 0.1% to about 10% by weight of at least one polyol as component B having more than six hydroxyl groups and having a number average molecular weight Mn of greater than 2000 g / mol; from about 0.05% to about 3% by weight of at least one sterically hindered phenolic antioxidant as component C; 0 wt% to about 3 wt% of at least one cationic polyethyleneimine branched polymer as component D; 0 wt% to about 50 wt% of at least one fibrous filler and / or particulate filler as component E; 0 wt% to about 25 wt% of further additives as component F; wherein the total weight% of component A to component F is 100 weight%.

Description

Cross-references to related applications

[0001] This application claims the benefit of priority to U.S. Provisional Patent Application No. 63 / 535,155, filed August 29, 2023, the contents of which are incorporated herein by reference in their entirety. Background Technology

[0002] Thermoplastic polyamides (such as PA6 and PA66) are often used as materials in the form of glass fiber reinforced molding compositions for parts that are exposed to elevated temperatures and / or humidity during their lifespan, accompanied by thermal oxidative degradation.

[0003] Various heat aging resistant additives, such as Cu-containing stabilizers, organic HALS (hindered amine light stabilizers) compounds, or combinations of sterically hindered phenols or polyols, are used in polyamide molding compositions to counteract or delay thermal oxidative degradation. Improving the heat aging resistance (HAR) of polyamides is highly desirable because it can result in longer lifespans of parts subjected to thermal stress or reduce the risk of structural failure. Furthermore, improved HAR can allow the use of such parts at higher temperatures.

[0004] The heat aging resistance of molding compositions is known to be unsatisfactory, especially when exposed to heat for extended periods. Furthermore, due to increased electrical charge, a growing number of applications require materials free of any halide-based stabilizer systems (e.g., copper iodide) due to the risk of corrosion and corresponding failure. Therefore, none of the compositions disclosed in the cited literature satisfies the requirement of good thermal stability while avoiding the use of widely used metal halide stabilizers.

[0005] Thermoplastic molding compositions without metal halide stabilizers have been previously studied (such as in U.S. Patent Application Publication No. 2023 / 0128646, the full text of which is incorporated herein by reference); however, there remains a need for thermoplastic molding compositions without metal halide that have improved retention of tensile and impact properties. Summary of the Invention

[0006] In some aspects, the technology described herein relates to a thermoplastic molding composition comprising: about 30% to about 99.9% by weight of at least one thermoplastic polyamide as component A; and about 0.1% to about 10% by weight of at least one polyol as component B, the polyol having more than six hydroxyl groups and having a number-average molecular weight M greater than 2000 g / mol. n; at least one sterically hindered phenolic antioxidant of about 0.05 wt% to about 3 wt% as component C; at least one cationic polyethyleneimine branched polymer of about 0.1 wt% to about 3 wt% as component D; at least one fiber filler and / or particulate filler of about 0 wt% to about 50 wt% as component E; and other additives of about 0 wt% to about 25 wt% as component F; wherein the total weight% of components A to F is 100 wt%.

[0007] In some respects, the technology described herein relates to a thermoplastic molding composition comprising about 45% to about 70% by weight of component A.

[0008] In some respects, the technology described herein relates to a thermoplastic molding composition wherein component A comprises polyamide 6 (PA6), polyamide 66 (PA66), polyamide 12 (PA12), polyamide 610 (PA610), polyamide 46 (PA46), or combinations thereof.

[0009] In some respects, the technology described herein relates to a thermoplastic molding composition comprising about 1% to about 5% by weight of component B.

[0010] In some respects, the technology described herein relates to a thermoplastic molding composition wherein component B comprises an ethylene vinyl alcohol copolymer.

[0011] In some respects, the technology described herein relates to a thermoplastic molding composition wherein component C comprises a phenol substituted with one or more of an alkyl group, an alkoxy group, a substituted amino group, or a combination thereof.

[0012] In some aspects, the technology described herein relates to a thermoplastic molding composition wherein component C comprises 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 3,5-di-tert-butyl-4-hydroxybenzylphosphonate distearate, 3,5-di-tert-butyl-4-hydroxyhydrogenated cinnamic acid-2,6,7-trioxa-1-phosphabicyclo[2.2.2]oct-4-methyl ester, 3,5 -di-tert-butyl-4-hydroxyphenyl-3,5-distearatethiotriazineamine, 2-(2'-hydroxy-3′-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2,6-di-tert-butyl-4-hydroxymethylphenol, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 4,4'-methylenebis(2,6-di-tert-butylphenol), 3,5-di-tert-butyl-4-hydroxybenzyldimethylamine, N,N'-hexamethylenebis-3,5-di-tert-butyl-4-hydroxyhydrocinnamate, or combinations thereof.

[0013] In some respects, the technology described herein relates to a thermoplastic molding composition comprising about 0.1% to about 1.5% by weight of component D.

[0014] In some respects, the technology described herein relates to a thermoplastic molding composition wherein component D has a number-average molecular weight Mn greater than about 1000 g / mol.

[0015] In some respects, the technology described herein relates to a thermoplastic molding composition wherein component D has a number-average molecular weight Mn of about 1300 g / mol.

[0016] In some respects, the technology described herein relates to a thermoplastic molding composition wherein component D has a cationic charge density of about 16 meq / g DS.

[0017] In some respects, the technology described herein relates to a thermoplastic molding composition comprising about 10% by weight to about 50% by weight of component E.

[0018] In some aspects, the technology described herein relates to a thermoplastic molding composition wherein component E comprises carbon fiber, glass fiber, glass beads, amorphous silica, calcium silicate, calcium metasilicate, magnesium carbonate, kaolin, chalk, powdered quartz, mica, barium sulfate, feldspar, aromatic polyamide fiber, potassium titanate fiber, kaolin, calcined kaolin, wollastonite, talc, chalk, layered nanofillers, needle-like nanofillers, boehmite, bentonite, montmorillonite, vermiculite, lithium montmorillonite, synthetic lithium saponite, or combinations thereof.

[0019] In some respects, the technology described herein relates to a thermoplastic molding composition wherein the thermoplastic molding composition retains at least about 85% of its tensile strength after aging at 180°C for 3000 hours.

[0020] In some respects, the technology described herein relates to a thermoplastic molding composition wherein the thermoplastic molding composition retains at least about 90% of its tensile strength after aging at 180°C for 3000 hours.

[0021] In some respects, the technology described herein relates to a thermoplastic molding composition wherein the thermoplastic molding composition retains at least about 60% of its tensile strength after aging at 180°C for 5000 hours.

[0022] In some respects, the technology described herein relates to a thermoplastic molding composition wherein the thermoplastic molding composition retains at least about 70% of its tensile strength after aging at 180°C for 5000 hours.

[0023] In some respects, the technology described herein relates to a thermoplastic molding composition wherein the thermoplastic molding composition retains at least about 55% of its tensile elongation at break after aging at 180°C for 3000 hours.

[0024] In some respects, the technology described herein relates to a thermoplastic molding composition wherein the thermoplastic molding composition retains at least about 65% of its tensile elongation at break after aging at 180°C for 3000 hours.

[0025] In some respects, the technology described herein relates to a thermoplastic molding composition wherein the thermoplastic molding composition retains at least about 40% of its tensile elongation at break after aging at 180°C for 5000 hours.

[0026] In some respects, the technology described herein relates to a thermoplastic molding composition wherein the notched Izod impact strength of the thermoplastic molding composition is retained at least about 95% after aging at 180°C for 3000 hours.

[0027] In some respects, the technology described herein relates to a thermoplastic molding composition wherein the notched Izod impact strength of the thermoplastic molding composition is at least about 90% retained after aging at 180°C for 5000 hours. Attached Figure Description

[0028] The aspects, features, benefits, and advantages of the embodiments described herein will become apparent from the following description, the appended claims, and the accompanying drawings, wherein:

[0029] Figure 1 This is a graph showing the retention rate of tensile strength of the composition disclosed herein after heat aging at 180°C for 5000 hours.

[0030] Figure 2 This is a graph showing the retention of tensile elongation of the composition disclosed herein after heat aging at 180°C for 5000 hours.

[0031] Figure 3 This is a graph showing the notched Izod impact retention rate of the composition disclosed herein after heat aging at 180°C for 5000 hours. Detailed Implementation

[0032] This disclosure describes thermoplastic molding compositions comprising polyamides that have improved heat aging resistance (HAR) and retain good mechanical properties after heat aging. The components disclosed herein can act as heat stabilizers in thermoplastic polyamide molding compositions and significantly improve heat aging resistance under prolonged exposure to heat.

[0033] In some embodiments, a thermoplastic molding composition is provided comprising: about 30% to about 99.9% by weight of at least one thermoplastic polyamide as component A; about 0.1% to about 10% by weight of at least one polyol as component B, the polyol having more than six hydroxyl groups and having a number-average molecular weight Mn greater than 2000 g / mol; about 0.05% to about 3% by weight of at least one sterically hindered phenolic antioxidant as component C; about 0.1% to about 3% by weight of at least one cationic polyethyleneimine branched polymer as component D; about 0% to about 50% by weight of at least one fiber filler and / or particulate filler as component E; and about 0% to about 25% by weight of other additives as component F; wherein the total weight percentage of components A to F is 100% by weight.

[0034] As disclosed in this article, the number-average molecular weight and weight-average molecular weight (Mi and Mj, respectively) n M w The molecular weight and polydispersity data can be obtained using gel permeation chromatography (GPC) with hexafluoroisopropanol as the solvent and PMMA calibration performed. This molecular weight determination can be used for all components of the thermoplastic molding compositions according to the invention.

[0035] In some embodiments, the thermoplastic molding composition comprises about 30% to about 99.9% by weight of at least one thermoplastic polyamide as component A. For example, the thermoplastic molding composition may comprise about 30%, about 35%, about 40%, about 45%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, about 85%, about 90%, about 95%, about 96%, about 97%, about 98%, about 99%, about 99.9% by weight, or any amount of component A within the range formed by any two of the foregoing values.

[0036] If component E or component F or a combination thereof is present in the thermoplastic molding composition, the maximum amount of component A minus the minimum amount of each of component E or component F or a combination thereof, such that the total weight percentage of components A to F is 100 by weight.

[0037] The intrinsic viscosity of the polyamide in the molding composition of the present invention, as determined according to ISO 307 in a 0.5% by weight solution of 96% by weight sulfuric acid at 25°C, is typically from 90 ml / g to 350 ml / g, preferably from 110 ml / g to 240 ml / g.

[0038] Specifically envisioned are semi-crystalline or amorphous resins with a molecular weight (weight average) of at least 5,000, such as those described in the following U.S. patents: U.S. Patent 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.

[0039] Examples of these polymers are polyamides derived from lactams having 7 to 13 ring members, such as polycaprolactam, polyoctyllactam, and polylaurolactam; and polyamides obtained by reacting dicarboxylic acids with diamines.

[0040] The dicarboxylic acids that can be used are alkane dicarboxylic acids and aromatic dicarboxylic acids having 6 to 12, particularly 6 to 10, carbon atoms. By way of example only, those dicarboxylic acids that may be mentioned here are adipic acid, azelaic acid, sebacic acid, dodecanoic acid, and terephthalic acid and / or isophthalic acid.

[0041] Particularly suitable diamines are alkane diamines having 6 to 12, especially 6 to 8, carbon atoms, as well as m-phenylenediamine, bis(4-aminophenyl)methane, bis(4-aminocyclohexyl)methane, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminocyclohexyl)propane and 1,5-diamino-2-methylpentane.

[0042] In some embodiments, preferred polyamides include polyhexamethylene hexadiamide, polyhexamethylene decanadiamide, and polycaprolactam, as well as nylon-6 / 6,6 copolyamides, particularly those having caprolactam units in proportions of 5% to 95% by weight (e.g., Ultramid from BASF SE). ® C31).

[0043] Other suitable polyamides can be obtained by so-called direct polymerization of ω-aminoalkyl nitrile (such as aminohexanonitrile (PA 6) and adiponitrile with hexamethylenediamine (PA 66)) in the presence of water, for example as described in DE-A 10313681, EP-A1198491 and EP 922065.

[0044] Also mentioned are polyamides (nylon-4,6) that can be obtained, for example, by condensation of 1,4-diaminobutane with adipic acid at elevated temperatures. Methods for preparing polyamides of this structure are described, for example, in EP-A 38094, EP-A 38582, and EP-A 39524.

[0045] Other suitable examples are polyamides that can be obtained by copolymerization of two or more of the above monomers, and mixtures of two or more polyamides in any desired mixing ratio. Particularly preferred are mixtures of nylon-6,6 with other polyamides, especially blends of nylon-6 and nylon-66, as well as nylon-6 / 6,6 copolyamides and nylon-6,6 / 6 copolyamides.

[0046] Other copolyamides that have proven particularly advantageous are semi-aromatic copolyamides, such as PA 6 / 6T and PA 66 / 6T, wherein the triamine content of these is less than 0.5% by weight, preferably less than 0.3% by weight (see EP-A 299444). Other high-temperature resistant polyamides are known from EP-A1994075 (PA 6T / 6I / MXD6).

[0047] The methods described in EP-A 129 195 and 129 196 can be used to prepare preferred semi-aromatic copolyamides with low triamine content.

[0048] The following incomplete list includes the polyamides (A) mentioned and other polyamides (A) used for the purposes of this disclosure, as well as monomers comprising:

[0049] AB polymer:

[0050] PA 4 pyrrolidone

[0051] PA 6ε-caprolactam

[0052] PA 7 Heptanolactam

[0053] PA 8 Octyllactam

[0054] PA 9,9-Aminononanoic acid

[0055] PA 11 11-Aminoundecanoic acid

[0056] PA 12 laurolactam

[0057] AA / BB polymer:

[0058] PA 46 Tetramethylenediamine, Adipic acid

[0059] PA 66 Hexamethylenediamine, adipic acid

[0060] PA 69 Hexamethylenediamine, Azelaic acid

[0061] PA 610 Hexamethylenediamine, sebacic acid

[0062] PA 612 Hexamethylenediamine, Decanedicarboxylic Acid

[0063] PA 613 Hexamethylenediamine, Undecanedicarboxylic Acid

[0064] PA 1212 1,12-Dodecanediamine, Decanedicarboxylic Acid

[0065] PA 1313 1,13-Diaminotridecane,undecanedicarboxylic acid

[0066] PA 6T Hexamethylenediamine, terephthalic acid

[0067] PA MXD6 m-Phenylenediamine, adipic acid

[0068] AA / BB polymer:

[0069] PA 6I (Hexamethylenediamine, isophthalic acid)

[0070] PA 6-3-T Trimethylhexamethylenediamine, terephthalic acid

[0071] PA 6 / 6T (See PA 6 and PA 6T)

[0072] PA 6 / 66 (See PA 6 and PA 66)

[0073] PA 6 / 12 (See PA 6 and PA 12)

[0074] PA 66 / 6 / 610 (See PA 66, PA 6 and PA 610)

[0075] PA 6I / 6T (See PA 6I and PA 6T)

[0076] PA PACM 12 Diaminodicyclohexylmethane, laurolactam

[0077] PA 6I / 6T / PACM as PA 6I / 6T + diaminodicyclohexylmethane

[0078] PA 12 / MACMI laurolactam, dimethyldiaminodicyclohexylmethane, isophthalic acid

[0079] PA 12 / MACMT laurolactam, dimethyldiaminodicyclohexylmethane, terephthalic acid

[0080] PA PDA-T phenylenediamine, terephthalic acid

[0081] The preferred options are PA 6, PA 66, PA 6 / 66, and PA 66 / 6.

[0082] Suitable copolyamides can be composed of the following substances:

[0083] A1) 20.0% to 90.0% by weight of units derived from terephthalic acid and hexamethylenediamine.

[0084] A2) 0% to 50.0% by weight of units derived from ε-caprolactam.

[0085] A3) 0% to 80.0% by weight of units derived from diacid and hexamethylenediamine.

[0086] A4) 0% to 40.0% by weight of other monomers forming polyamides,

[0087] The proportion of component A2), component A3), component A4), or mixtures thereof is at least 10.0% by weight.

[0088] Component A1) contains 20.0% to 90.0% by weight of units derived from terephthalic acid and hexamethylenediamine.

[0089] In addition to units derived from terephthalic acid and hexamethylenediamine, the copolyamide optionally includes units derived from ε-caprolactam and / or units derived from diacid and hexamethylenediamine and / or units derived from other monomers that form the polyamide.

[0090] Aromatic dicarboxylic acids (A4) contain 8 to 16 carbon atoms. Suitable aromatic dicarboxylic acids include, for example, isophthalic acid, substituted terephthalic acid and isophthalic acid, such as 3-tert-butylisophthalic acid; polycyclic dicarboxylic acids, such as 4,4'-diphenyldicarboxylic acid and 3,3'-diphenyldicarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid and 3,3'-diphenylmethanedicarboxylic acid, 1,4-naphthalenedicarboxylic acid or 2,6-naphthalenedicarboxylic acid, phenoxyterephthalic acid, and isophthalic acid is particularly preferred.

[0091] Other monomers forming polyamides (A4) can be derived from dicarboxylic acids having 4 to 16 carbon atoms and aliphatic or alicyclic diamines having 4 to 16 carbon atoms, as well as aminocarboxylic acids / corresponding lactams having 7 to 12 carbon atoms. Examples of suitable monomers of these types mentioned are octanoic acid, azelaic acid, and sebacic acid as representatives of aliphatic dicarboxylic acids; 1,4-butanediamine, 1,5-pentanediamine, piperazine, 4,4'-diaminodicyclohexylmethane, 2,2-(4,4'-diaminodicyclohexyl)propane, and 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane or m-phenylenediamine as representatives of diamines; and caprolactam, heptanolactam, ω-aminoundecanoic acid, and laurolactam as representatives of lactams / aminocarboxylic acids. Suitable copolyamides of this type are described in more particular detail in DE-A-10 2009011668.

[0092] In some embodiments, component A includes polyamide 6 (PA6), polyamide 66 (PA66), polyamide 12 (PA12), polyamide 610 (PA610), polyamide 46 (PA46), or combinations thereof.

[0093] In some embodiments, the thermoplastic molding composition comprises about 0.1% to about 10% by weight of at least one polyol as component B, the polyol having more than six hydroxyl groups and having a number-average molecular weight M greater than 2000 g / mol. n For example, a thermoplastic molding composition may contain component B in amounts of about 0.1 wt%, about 0.2 wt%, about 0.3 wt%, about 0.4 wt%, about 0.5 wt%, about 1 wt%, about 2 wt%, about 3 wt%, about 4 wt%, about 5 wt%, about 6 wt%, about 7 wt%, about 8 wt%, about 9 wt%, about 10 wt%, or any amount of any two of the foregoing values.

[0094] In some embodiments, component B comprises at least one polyol having more than 6 hydroxyl groups and a number-average molecular weight M greater than 2000 g / mol.n Component B may have more than 8 or more than 10 hydroxyl groups.

[0095] In some embodiments, component B has a number-average molecular weight M greater than 3000 g / mol, such as greater than 5000 g / mol, or greater than 10000 g / mol. n The maximum number-average molecular weight is preferably 35,000 g / mol, more preferably 25,000 g / mol. Particularly preferred component B has a number-average molecular weight of 10,000 g / mol to 30,000 g / mol, more preferably 12,500 g / mol to 22,500 g / mol, and most preferably 15,000 g / mol to 20,000 g / mol.

[0096] Weight average M w Preferably, the concentration is 10,000 g / mol to 250,000 g / mol, more preferably 25,000 g / mol to 120,000 g / mol, and particularly 30,000 g / mol to 80,000 g / mol.

[0097] Component B can be selected from any suitable polyols, provided they have more than 6 hydroxyl groups and a number-average molecular weight M greater than 2000 g / mol. n A suitable example of a polyol is an ethylene-vinyl alcohol copolymer, which can be produced by Mitsubishi Chemical under the trade name Soarnol. ™ Or it can be produced by Kuraray under the brand name EVAL ™ Commercially available. In some implementations, other high molecular weight polyols may also be suitable.

[0098] In some embodiments, component B is an ethylene-vinyl alcohol copolymer. Preferably, in the ethylene-vinyl alcohol copolymer, the content of ethylene units is 10 mol% to 60 mol%, more preferably 20 mol% to 50 mol%, and particularly 25 mol% to 50 mol%.

[0099] In addition to ethylene and vinyl alcohol, the copolymer may contain residual vinyl acetate, preferably 20 mol% or less, more preferably 10 mol% or less, and particularly 5 mol% or less. Most preferably, there is no residual vinyl acetate. The ethylene-vinyl alcohol copolymer can be obtained by partial or complete hydrolysis of the ethylene-vinyl acetate copolymer.

[0100] The number-average molecular weight M of particularly suitable ethylene-vinyl alcohol copolymers nThe molecular weight is 10,000 g / mol to 30,000 g / mol, more preferably 12,500 g / mol to 22,500 g / mol, and most preferably 15,000 g / mol to 20,000 g / mol. Most preferably, it has a number-average molecular weight Mn of 18,000 g / mol and a weight-average molecular weight Mw of 50,000 g / mol.

[0101] Polyols may also contain additional functional groups that are not hydroxyl groups. However, preferably, polyols contain only hydroxyl groups as functional groups. Polyols can be linear, branched, or hyperbranched. Specifically, highly branched or hyperbranched structures partially composed of hydroxyl functional groups, as described in EP 2227507 B1 and DE102004051241 A1, are also suitable for achieving the desired effect. For example, highly branched or hyperbranched polyetheramines with hydroxyl values ​​of 50 mg KOH / g to 1000 mg KOH / g, preferably 100 mg KOH / g to 900 mg KOH / g, and more preferably 150 mg KOH / g to 800 mg KOH / g can be used.

[0102] In some embodiments, the thermoplastic molding composition comprises about 0.05 wt% to about 3 wt% of at least one sterically hindered phenolic antioxidant as component C. For example, the thermoplastic molding composition may comprise about 0.05 wt%, about 0.1 wt%, about 0.5 wt%, about 1 wt%, about 1.5 wt%, about 2 wt%, about 2.5 wt%, about 3 wt%, or any amount of component C within a range formed by any two of the foregoing values.

[0103] In some embodiments, component C has a molecular weight greater than 500 g / mol, such as greater than 1000 g / mol. Additionally, component C should preferably exhibit high thermal stability, such as a maximum weight loss of 5%, more preferably a maximum weight loss of 2%, as measured in a TGA (thermogravimetric analysis) experiment under nitrogen at 300°C (from 40°C to 120°C at 10°C / min, isothermal for 15 minutes at the latter temperature, followed by an increase in temperature from 120°C to 600°C at 20°C / min).

[0104] Component C preferably has at least one, more preferably at least two, branches of at least one C. 3-12 The alkyl-substituted phenolic group acts as a sterically hindered group. The substituted phenolic group is covalently linked to the structure of component C.

[0105] Suitable sterically hindered phenols for component C are, in principle, all compounds having a phenolic structure and at least one bulky group on the phenolic ring. The bulky group is, for example, a branched C. 3-12 -alkyl group, preferably branched C 3-6 -alkyl group, more preferably isopropyl or tert-butyl group.

[0106] In some embodiments, compounds of, for example, the following formula are preferably used:

[0107]

[0108] Where R 1 and R 2 Each is an alkyl group, a substituted alkyl group, or a substituted triazole group, wherein group R is an alkyl group, a substituted alkyl group, or a substituted triazole group. 1 and R 2 They can be the same or different, and R 3 It is an alkyl group, a substituted alkyl group, an alkoxy group, or a substituted amino group. The alkyl and alkoxy residues preferably have 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms. The substituent is preferably C. 1-12 -alkyl, more preferably C 1-6 -alkyl, C is the most preferred. 1-4 -alkyl. R 1 To R 3 At least one of them is preferably a bulky group as defined above.

[0109] The types of antioxidants mentioned above are described, for example, in DE-A 2702661 (US Patent No. 4,360,617).

[0110] Another preferred group of sterically hindered phenols are provided by groups derived from substituted phenyl carboxylic acids, particularly those derived from substituted phenyl propionic acids, which preferably have at least one bulky group on the phenyl group. The group contains in its structure at least one, preferably two, covalently linked substituted phenyl carboxylic acid units, which preferably have at least one bulky group on the phenyl group.

[0111] Preferred phenylcarboxylic acids are phenyl-C 1-12 -carboxylic acid, more preferably phenyl-C 2-6 -Carboxylic acid. As described above, the phenyl group is preferably a phenolic group having at least one bulky group on the phenolic ring. Therefore, the above-mentioned sterically hindered phenol is preferably with C 1-12 -Alkyl carboxylic acid, more preferably straight-chain C 2-6 -Alkane carboxylic acid covalently linked.

[0112] These particularly preferred compounds are those with the following formula:

[0113]

[0114] Where R 4 R 5 R 7 and R 8Each group is an independent C1-C8 alkyl group, which may itself have substitutions (at least one of these groups is a bulky group), and R 6 It is a divalent aliphatic group having 1 to 10 carbon atoms and whose main chain may also have CO bonds. R 4 To R 8 At least one of them is a bulky group as defined above.

[0115] The preferred compounds corresponding to these formulas are:

[0116]

[0117] (Irganox from BASF SE) ® 245)

[0118]

[0119] (Irganox from BASF SE) ® 259)

[0120] As examples of sterically hindered phenols that can be included as component C in the compositions disclosed herein, all of the following substances should be mentioned:

[0121] 2,2'-Methylenebis(4-methyl-6-tert-butylphenol), 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (from Irganox of BASF SE) ® 1010), 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid distearate, 3,5-di-tert-butyl-4-hydroxyhydrogenated cinnamic acid 2,6,7-trioxa-1-phosphabicyclo[2.2.2]oct-4-ylmethyl ester, 3,5-di-tert-butyl-4-hydroxyphenyl-3,5-distearate-thiotriazolylamine, 2-(2'-hydroxy-3'-hydroxy-3',5'-di-tert-butylphenyl)-5-chloro-benzotriazole, 2,6-di-tert-butyl-4-hydroxymethylphenol, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-benzene, 4,4'-methylenebis(2,6-di-tert-butylphenol), 3,5-di-tert-butyl-4-hydroxybenzyl dimethylamine.

[0122] Not wanting to be bound by theory, the compounds that have proven particularly effective and are therefore preferred are 2,2'-methylenebis(4-methyl-6-tert-butylphenol) and 1,6-hexanediol bis(3,5-di-tert-butyl-4-hydroxyphenyl) propionate (Irganox). ®259), pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and N,N'-hexamethylenebis-3,5-di-tert-butyl-4-hydroxyhydrocinnamate (Irganox) ® 1098) and the aforementioned Irganox product from BASF SE ® 245 and Irganox ® 1010, they have particularly good applicability.

[0123] In some cases, sterically hindered phenols having no more than one steric group adjacent to the phenolic hydroxyl group have proven particularly advantageous; especially when evaluating color fastness during long-term storage in diffuse light.

[0124] In some embodiments, the thermoplastic molding composition comprises about 0.1 wt% to about 3 wt% of at least one cationic polyethyleneimine branched polymer as component D. For example, the thermoplastic molding composition may comprise about 0.1 wt%, about 0.5 wt%, about 1 wt%, about 1.5 wt%, about 2 wt%, about 2.5 wt%, about 3 wt%, or any amount of component D within a range formed by any two of the foregoing values.

[0125] In some implementations, the number-average molecular weight M of component D n It is greater than about 1000 g / mol, such as about 1050 g / mol, about 1100 g / mol, about 1150 g / mol, about 1200 g / mol, about 1250 g / mol, about 1300 g / mol, about 1350 g / mol, about 1400 g / mol, or any value contained within the range formed by any two of the foregoing values.

[0126] In some embodiments, the cation charge density of component D is from about 10 meq / g DS to about 20 meq / g DS, such as about 10 meq / g DS, about 11 meq / g DS, about 12 meq / g DS, about 13 meq / g DS, about 14 meq / g DS, about 15 meq / g DS, about 16 meq / g DS, about 17 meq / g DS, about 18 meq / g DS, about 19 meq / g DS, about 20 meq / g DS, or any value contained within the range formed by any two of the foregoing values.

[0127] In some embodiments, the polyethyleneimine may be selected from highly branched polyethyleneimine. Highly branched polyethyleneimine is characterized by its high degree of branching (DB). The degree of branching can be, for example, determined by… 13 C-NMR spectroscopy, preferably performed in D2O, is defined as follows:

[0128] DB = D + T / D + T + L

[0129] Where D (dendritic) corresponds to the fraction of tertiary amino groups, L (linear) corresponds to the fraction of secondary amino groups, and T (terminal) corresponds to the fraction of primary amino groups.

[0130] In the context of this disclosure, highly branched polyethyleneimine is polyethyleneimine with a DB of 0.25 to 0.90.

[0131] In some embodiments, polyethyleneimine is selected from copolymers of ethyleneimine, such as copolymers of ethyleneimine with at least one diamine having two NH2 groups per molecule other than ethyleneimine (e.g., copolymers of propyleneimine) or with at least one compound having three NH2 groups per molecule (e.g., melamine).

[0132] Suitable compounds that can be used as component D include, but are not limited to, Lupasol from BASF. ® G 20 WF.

[0133] Not wishing to be bound by theory, in some embodiments, components B and D can induce a synergistic effect that allows for high performance and strong retention of tensile strength, elongation at break, and notched Izod impact strength in the compositions of this disclosure. In some embodiments, compositions of this disclosure containing both components B and D achieve improved performance compared to compositions containing only one of components B or D.

[0134] In some embodiments, the thermoplastic molding composition comprises 0% to about 50% by weight of at least one fiber filler and / or particulate filler as component E. In some embodiments, the thermoplastic molding composition comprises 0% by weight of component E, such that component E is omitted. In other embodiments, the thermoplastic molding composition comprises about 1% by weight, about 5% by weight, about 10% by weight, about 15% by weight, about 20% by weight, about 25% by weight, about 30% by weight, about 35% by weight, about 40% by weight, about 45% by weight, about 50% by weight, or an amount of component E comprising any value within the range formed by any two of the foregoing values.

[0135] In some embodiments, component E includes carbon fibers, glass fibers, glass beads, amorphous silica, calcium silicate, calcium metasilicate, magnesium carbonate, kaolin, chalk, powdered quartz, mica, barium sulfate, feldspar, or combinations thereof. Preferred fiber fillers include carbon fibers, aramid fibers, and potassium titanate fibers, with glass fibers in glass form being particularly preferred. These can be used as rovings or in the form of commercially available chopped glass.

[0136] Fiber fillers can be surface-pretreated with silane compounds to improve their compatibility with thermoplastic materials. Suitable silane compounds have the following general formula:

[0137] (X–(CH2) n ) k –Si–(O–C m H 2m+1 ) 4–k

[0138] The substituents are defined as follows:

[0139] X = NH2, epoxide, or OH.

[0140] n is an integer from 2 to 10, preferably from 3 to 4.

[0141] m is an integer from 1 to 5, preferably from 1 to 2, and

[0142] k is an integer from 1 to 3, preferably 1.

[0143] Preferred silane compounds are aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane, and aminobutyltriethoxysilane, as well as corresponding silanes containing a glycidyl group as substituent X.

[0144] The amount of silane compound typically used for surface coating is 0.01% to 2% by weight, preferably 0.025% to 1.0% by weight, and particularly 0.05% to 0.5% by weight (based on the weight of component E).

[0145] Needle-shaped mineral fillers are also suitable. For the purposes of this invention, needle-shaped mineral fillers are mineral fillers with strongly developed needle-like characteristics. An example is needle-shaped wollastonite. The mineral preferably has an L / D (length to diameter) ratio of 8:1 to 35:1, more preferably 8:1 to 11:1. The mineral filler may optionally be pretreated with the aforementioned silane compound, but pretreatment is not required.

[0146] Other fillers that may be mentioned include kaolin, calcined kaolin, wollastonite, talc, and chalk, as well as layered or needle-like nanofillers, preferably in amounts of 0.1% to 10%. Preferred materials for this purpose are boehmite, bentonite, montmorillonite, vermiculite, lithium montmorillonite, and synthetic lithium saponite. The layered nanofillers are organically modified using existing methods to ensure good compatibility with organic binders. Adding layered or needle-like nanofillers to the nanocomposite materials of the present invention further improves mechanical strength.

[0147] In some embodiments, the thermoplastic molding composition contains 0% to about 25% by weight of other additives as component F. For example, in some embodiments, the thermoplastic molding composition may contain 0% by weight of component F, such that component F is omitted, or may contain about 1% by weight, about 5% by weight, about 10% by weight, about 15% by weight, about 20% by weight, about 25% by weight, or any amount of component F within the range formed by any two of the foregoing values.

[0148] If other additives are used, the minimum amount is preferably 0.1% by weight, more preferably 0.25% by weight, and most preferably 0.5% by weight.

[0149] The thermoplastic molding composition of the present invention may contain conventional processing aids, other stabilizers, oxidation inhibitors, agents that resist thermal decomposition and UV decomposition, lubricants and release agents, colorants (such as dyes and pigments), nucleating agents, plasticizers, etc., as component E.

[0150] The thermoplastic molding compositions disclosed herein may contain about 0.05% to about 3% by weight, preferably about 0.1% to about 1.5% by weight, and particularly about 0.1% to about 1% by weight of a lubricant as component F.

[0151] Preferred are salts of aluminum, alkali metals, or alkaline earth metals, or esters or amides of fatty acids having 10 to 44 carbon atoms, preferably 12 to 44 carbon atoms. The metal ions are preferably alkaline earth metals and aluminum, with calcium or magnesium being particularly preferred.

[0152] Preferred metal salts include calcium stearate and calcium lignite, as well as aluminum stearate. Mixtures of various salts in any desired mixing ratio may also be used.

[0153] In some embodiments, the molding composition of the present invention may contain, as component F, about 0.05% to about 3% by weight, preferably about 0.1% to about 1.5% by weight, and particularly about 0.1% to about 1% by weight of a copper stabilizer, preferably a Cu(I) halide, particularly a mixture with an alkali metal halide, preferably KI, in particular at a ratio of 1:4, or a sterically hindered phenol, or a mixture thereof.

[0154] In some embodiments, the carboxylic acids disclosed herein may be mono- or di-carboxylic. Examples that may be mentioned are nonanoic acid, palmitic acid, lauric acid, heptadecanic acid, dodecanoic acid, benzalkonium chloride, and stearic acid, decanoic acid, and linalic acid (a mixture of fatty acids having 30 to 40 carbon atoms) are particularly preferred.

[0155] In some embodiments, the aliphatic alcohols disclosed herein can be mono- to tetra-membered. Examples of alcohols are n-butanol, n-octanol, stearyl alcohol, ethylene glycol, propylene glycol, neopentyl glycol, pentaerythritol, and preferably glycerol and pentaerythritol.

[0156] In some embodiments, the aliphatic amines disclosed herein can be mono- or ternary. Examples of such aliphatic amines are stearylamine, ethylenediamine, propylenediamine, hexamethylenediamine, and di(6-aminohexyl)amine, with ethylenediamine and hexamethylenediamine being particularly preferred. Preferred esters or amides are, respectively, glyceryl distearate, glyceryl tristearate, ethylenediamine distearate, glyceryl monopalmitate, glyceryl trilaurate, glyceryl monobenzyl heatherate, and pentaerythritol tetrastearate.

[0157] Mixtures of various esters or amides can also be used, or combinations of esters and amides in any desired mixing ratio can be used.

[0158] According to a preferred embodiment of the invention, the molding composition is free of copper, specifically free of copper stabilizers such as Cu / (I) halides, and combinations of Cu(I) halides and alkali metal halides.

[0159] More preferably, the thermoplastic molding composition of the present invention is free of metal halides. Systems free of metal halides, i.e., so-called electrofriendly systems, are of great interest because electromobility, electrification, and connectivity are an increasing trend in almost all industries. Therefore, in some embodiments, the thermoplastic molding composition is preferably free of metal halides, specifically copper halides and alkali metal halides. In some embodiments, the metal halides are present in very low amounts. For example, the metal halides may be present from about 0.001% by weight to about 1% by weight.

[0160] Examples of other conventional additives F are an amount of up to about 25% by weight, preferably up to about 20% by weight, of an elastomeric polymer (also commonly referred to as an impact modifier, elastomer, or rubber).

[0161] If component D is used in the molding composition according to the invention, the elastomeric polymer disclosed herein with respect to component F is different from that of component D. Therefore, in the case where the composition contains component D, the polymer of component F, in particular the elastomeric polymer, is different from the polymer of component D. Similarly, the polymer of component F is different from the polymer of component B.

[0162] These are typically copolymers preferably composed of at least two of the following monomers: ethylene, propylene, butadiene, isobutylene, isoprene, chloroprene, vinyl acetate, styrene, acrylonitrile, and acrylates and / or methacrylates having 1 to 18 carbon atoms in the alcohol component.

[0163] Such polymers are described, for example, in Houben-Weyl, Methoden der organischen Chemie, Vol. 14 / 1 (Georg-Thieme-Verlag, Stuttgart, Germany, 1961), pp. 392–406, and in a special paper in CB Bucknall, Toughened Plastics (Applied Science Publishers, London, UK, 1977).

[0164] Preferred types of such elastomers are those known as ethylene-propylene (EPM) rubber and ethylene-propylene-diene (EPDM) rubber. EPM rubber typically does not actually have residual double bonds, while EPDM rubber can have 1 to 20 double bonds per 100 carbon atoms.

[0165] Examples of diene monomers for EPDM rubber that may be mentioned are conjugated dienes, such as isoprene and butadiene; non-conjugated dienes having 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, cyclohexadiene, cyclooctadiene, and dicyclopentadiene; and alkenyl norbornene, such as 5-ethylidene-2-norbornene, 5-butylidene-2-norbornene, 2-methylallyl-5-norbornene, and 2-isopropenyl-5-norbornene; and tricyclic dienes, such as 3-methyltricyclo[5.2.1.02,6]-3,8-decadiene; and mixtures thereof. 1,5-hexadiene, 5-ethylidene norbornene, and dicyclopentadiene are preferred. Based on the total weight of the rubber, the diene content of EPDM rubber is preferably from 0.5% to 50% by weight, particularly from 1% to 8% by weight.

[0166] EPM and EPDM rubbers may also preferably be grafted with reactive carboxylic acids or their derivatives. Examples of these are acrylic acid, methacrylic acid, and their derivatives, such as glycidyl (meth)acrylate and maleic anhydride.

[0167] Copolymers of ethylene with acrylic acid and / or methacrylic acid and / or esters of these acids are another group of preferred rubbers. The rubber may also contain dicarboxylic acids, such as maleic acid and fumaric acid, or derivatives of these acids, such as esters and anhydrides, and / or monomers containing epoxy groups. These dicarboxylic acid derivatives or epoxy-containing monomers are preferably incorporated into the rubber by adding monomers containing dicarboxylic acid groups and / or epoxy groups and having general formula I, II, III, or IV to a monomer mixture.

[0168]

[0169] Where R 1 To R 9 It is hydrogen or an alkyl group having 1 to 6 carbon atoms, where m is an integer from 0 to 20, g is an integer from 0 to 10, and p is an integer from 0 to 5. Group R 1 To R 9 Preferably, the hydrogen is present, 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.

[0170] Preferred compounds of formulas I, II, and IV are maleic acid, maleic anhydride, and (meth)acrylates containing epoxy groups (such as glycidyl acrylate and glycidyl methacrylate), as well as esters with tertiary alcohols (such as tert-butyl acrylate). Although the latter do not have a free carboxyl group, they behave similarly to free acids, and therefore they are referred to as monomers with a potential carboxyl group.

[0171] The copolymer is advantageously composed of 50% to 98% by weight of ethylene, 0.1% to 20% by weight of monomers containing epoxy groups and / or methacrylic acid and / or monomers containing anhydride groups, with the balance being (meth)acrylate.

[0172] Copolymers comprising the following components are particularly preferred: 50% to 98% by weight, particularly 55% to 95% by weight, of ethylene; 0.1% to 40% by weight, particularly 0.3% to 20% by weight, of glycidyl acrylate and / or glycidyl methacrylate, (meth)acrylic acid and / or maleic anhydride; and 1% to 45% by weight, particularly 5% to 40% by weight, of n-butyl acrylate and / or 2-ethylhexyl acrylate.

[0173] Other preferred (meth)acrylates are methyl acrylate, ethyl acrylate, propyl acrylate, isobutyl acrylate, and tert-butyl acrylate. Comonomers that can be used with these include vinyl esters and vinyl ethers.

[0174] The above-mentioned ethylene copolymers can be prepared by methods known per se, preferably by random copolymerization under high pressure and high temperature. Suitable methods are well known.

[0175] Other preferred elastomers are emulsion polymers, the preparation of which is described, for example, by Blackley in his monograph "Emulsion Polymerization". The emulsifiers and catalysts that can be used are known in themselves.

[0176] In principle, elastomers with a homogeneous structure or those with a shell structure can be used. The shell type structure is determined by the order in which the monomers are added. The morphology of the polymer is also affected by this order of addition.

[0177] The monomers mentioned here, by way of example only, used for the preparation of the rubber portion of the elastomer are acrylates, such as n-butyl acrylate and 2-ethylhexyl acrylate, the corresponding methacrylates, butadiene and isoprene, and mixtures thereof.

[0178] These monomers can be copolymerized with other monomers (such as styrene, acrylonitrile, vinyl ether) and with other acrylates or methacrylates (such as methyl methacrylate, methyl acrylate, ethyl acrylate or propyl acrylate).

[0179] The soft or rubbery phase of an elastomer (with a glass transition temperature below 0°C) can be a core, an outer cladding, or an intermediate shell (in cases where the elastomer has more than two shells). An elastomer with more than one shell can also have more than one shell composed of a rubbery phase.

[0180] If the elastomer structure contains one or more hard components (glass transition temperature above 20°C) in addition to the rubber phase, these hard components are typically prepared by polymerizing styrene, acrylonitrile, methacrylonitrile, α-methylstyrene, p-methylstyrene, or acrylates or methacrylates (such as methyl acrylate, ethyl acrylate, or methyl methacrylate) as the main monomers. Other comonomers can also be used in relatively small proportions.

[0181] UV stabilizers that may be mentioned are various substituted resorcinols, salicylates, benzotriazoles and benzophenones, which are typically used in amounts up to about 2 by weight based on the molding composition.

[0182] Materials that can be added as colorants include inorganic pigments such as titanium dioxide, ultramarine, iron oxide, and carbon black; organic pigments such as phthalocyanine, quinacridone, and perylene; and dyes such as anthraquinone.

[0183] Materials that can be used as nucleating agents include sodium phenylphosphinate, alumina, silica, and preferably talc.

[0184] The thermoplastic molding composition may further contain a flame retardant as component F.

[0185] As component F, the thermoplastic molding composition of this disclosure may contain 1.0 wt% to 10.0 wt%, preferably 2.0 wt% to 6.0 wt%, particularly 3.0 wt% to 5.0 wt% of at least one phosphazene of general formula (IX) or (X) as a flame retardant.

[0186] In some embodiments, component F comprises a mixture of cyclic phenoxyphosphazenes having three and four phenoxyphosphazene units. The weight ratio of rings containing three phenoxyphosphazene units to rings containing four phenoxyphosphazene units is preferably about 80:20. Larger rings of phenoxyphosphazene units may also be present, but in smaller quantities. Suitable cyclic phenoxyphosphazenes are available from Fushimi Pharmaceutical Co., Ltd. under the name Rabitle. ® FP-100 is obtained. It is a matte white / pale yellow solid with a melting point of 110°C, a phosphorus content of 13.4%, and a nitrogen content of 6.0%. In some embodiments, the proportion of rings having three phenoxyphosphazene units is at least 80.0% by weight.

[0187] The thermoplastic molding material preferably contains 1.0% to 6.0% by weight, preferably 2.5% to 5.5% by weight, and particularly 3.0% to 5.0% by weight of at least one aliphatic or aromatic ester of phosphoric acid or polyphosphoric acid as a flame retardant.

[0188] For this reason, solid, non-migratory phosphate esters with melting points between 70°C and 150°C are preferred. It is undesirable to be bound by theory; products from such phosphate esters are readily quantifiable and exhibit significantly less migration in molding materials. Particularly preferred examples are commercially available phosphate ester PX-200 (CAS: 139189-30-3) from Daihachi, or Sol-DP from ICL-IP. Other phosphate esters with appropriate phenyl group substitution are possible when this allows for reaching the preferred melting range. The general structural formula is as follows, depending on the ortho or para substitution pattern on the aromatic ring:

[0189]

[0190] in:

[0191] R 1 =H, methyl, ethyl or isopropyl, but preferably H.

[0192] n = is between 0 and 7, but preferably 0.

[0193] R 2-6 =H, methyl, ethyl, or isopropyl, but preferably methyl. R 6 Preferably with R 4 and R5 same.

[0194] m can be, but does not have to be, the same and is between 1, 2, 3, 4 and 5, but preferably 2.

[0195] R" can be H, methyl, ethyl or cyclopropyl, but preferably methyl and H.

[0196] It is particularly preferred when using an aromatic ester of at least one polyphosphate. Such aromatic polyphosphates can be obtained, for example, from Daihachi Chemical under the name PX-200.

[0197] As component F, the thermoplastic molding material according to the invention may contain 5.0 wt% to 30.0 wt%, preferably 10.0 wt% to 25.0 wt%, particularly 12.0 wt% to 20.0 wt%, for example about 16.0 wt%, of at least one metal phosphite or hypophosphite described below as a flame retardant. Examples of preferred flame retardants for component E are metal phosphites derived from hypophosphite. For example, metal salts of hypophosphite with Mg, Ca, Al, or Zn as metals can be used. Aluminum hypophosphite is particularly preferred here.

[0198] Phosphates of formula (I) and / or phosphates of formula (II) or their polymers are also suitable.

[0199]

[0200] Where R 1 and R 2 They are the same or different, and represent hydrogen, straight-chain or branched C1-C6-alkyl and / or aryl groups;

[0201] R 3 C1-C represents a straight chain or a branched chain. 10 -alkylene, C6-C 10 -arylene, -alkylarylene or -arylalkylene;

[0202] M represents Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, K and / or protonated nitrogen bases;

[0203] m = 1 to 4; n = 1 to 4; x = 1 to 4, preferably m = 3 and x = 3.

[0204] Preferably, R 1 R 2 Same or different, and represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl and / or phenyl.

[0205] Preferably, R3 This indicates methylene, ethylene, n-propylene, isopropylene, n-butylene, tert-butylene, n-pentylene, n-octylene or n-dodecylene, phenylene or naphthylene; methylphenylene, ethylphenylene, tert-butylphenylene, methylnaphthylene, ethylnaphthylene or tert-butylnaphthylene; phenylmethylene, phenylethylene, phenylpropylene or phenylbutylene.

[0206] Particularly preferred, R 1 R 2 It is hydrogen, methyl or ethyl, and M is Al; aluminum hypophosphite is particularly preferred.

[0207] Other flame retardants are, for example, halogenated flame retardants. Suitable halogenated flame retardants are preferably brominated compounds, such as brominated diphenyl ether, trimethylphenyl indene bromide (FR 1808 from DSB), tetrabromobisphenol A, and hexabromocyclododecane. Suitable flame retardants are preferably brominated compounds, such as brominated oligocarbonates (BC 52 or BC58 from Great Lakes).

[0208] Brominated oligostyrene, preferably used as a flame retardant, has an average degree of polymerization (number average) of 3 to 90, preferably 5 to 60, as measured by vapor pressure osmotic pressure determination in toluene. Cyclic oligomers are also suitable.

[0209] In some embodiments, halogenated flame retardants are not used in the thermoplastic molding composition. Suitable flame retardants as component F include melamine compounds, such as those that, when added to glass fiber-filled polyamide molding materials, reduce flammability and affect combustion behavior in a flame-retardant manner, resulting in improved properties in UL94 and glow wire tests.

[0210] The melamine compound may be selected, for example, from melamine borate, melamine phosphate, melamine sulfate, melamine pyrophosphate, melamine, melamine, cyanuramide, or melamine cyanurate, or mixtures thereof. According to the invention, the melamine cyanurate preferably suitable is the reaction product of melamine and cyanuric acid / isocyanuric acid in equimolar amounts.

[0211] Other suitable compounds (often described as salts or adducts) are melamine sulfate, melamine, melamine borate, oxalate, phosphate prim., phosphate sec., and pyrophosphate sec., and melamine neopentyl glycol borate. In some embodiments, the molding material is preferably free of polymeric melamine phosphate (CAS No. 56386-64-2 or 218768-84-4).

[0212] This should be understood as referring to melamine polyphosphates of 1,3,5-triazine compounds having an average degree of condensation (n) of 20 to 200, and a 1,3,5-triazine content of 1.1 to 2.0 moles per mole of phosphorus atoms, selected from the group consisting of melamine, melamine, cyanuramide, cyanuric acid diamide, cyanuric acid monoamide, 2-ureidomelamine, acetylguanidine, benzoguanidine, and diaminophenyltriazine. Preferably, the n value of such salts is typically 40 to 150, and the ratio of 1,3,5-triazine compound per mole of phosphorus atoms is preferably 1.2 to 1.8. Furthermore, the pH of the aqueous slurry of 10% by weight of the salt prepared according to EP-B1 095030 is typically greater than 4.5, and preferably at least 5.0. The pH is typically determined by adding 25g of salt and 225g of water to a 300ml beaker at 25°C, stirring the resulting aqueous slurry for 30 minutes, and then measuring the pH. The n-value (i.e., number-mean condensation degree) mentioned above can be determined using... 31 P solid-state NMR determination. JR van Wazer, CFCallis, J. Shoolery and R. Jones, J. Am. Chem. Soc., 78, 5715, 1956 disclosed that the number of adjacent phosphate groups gives a unique chemical shift, which allows for a clear distinction between orthophosphates, pyrophosphates and polyphosphates.

[0213] Another suitable functional polymer for use as component F is a flame-retardant polymer. Such polymers are described in U.S. Patent No. 8,314,202 and contain repeating units of 1,2-bis[4-(2-hydroxyethoxy)phenyl]acetone. Another suitable functional polymer for increasing char content comprises poly(2,6-dimethyl-1,4-phenylene ether) (PPPO).

[0214] The thermoplastic molding compositions of the present invention can be produced by methods known per se, by mixing the starting components in conventional mixing equipment (such as a screw-based extruder, Brabender mixer, or Banbury mixer) and then extruding them. After extrusion, the extrudate can be cooled and granulated. Alternatively, the individual components can be premixed, followed by the addition of the remaining starting materials, separately and / or similarly, as a mixture. The mixing temperature is typically from about 230°C to about 320°C.

[0215] These materials are suitable for producing any type of fiber, foil, and molded product. Some examples include: cylinder heads, motorcycle covers, intake manifolds, supercharger cooler covers, plug connectors, gears, cooling fan wheels, and coolant tanks.

[0216] In the electrical and electronic fields, improved flow polyamides can be used to produce plugs, plug components, 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 bundle components, circuit mounts, circuit mount assemblies, three-dimensional injection molded circuit mounts, electrical connection elements, and electromechanical components.

[0217] Possible uses within a vehicle include dashboards, steering column switches, seat components, headrests, center consoles, gearbox components, and door modules. Possible uses outside a vehicle include door handles, exterior mirror components, windshield wiper components, windshield wiper protective housings, grilles, roof rails, sunroof frames, engine hoods, cylinder head covers, intake pipes (especially intake manifolds), windshield wipers, and exterior body components.

[0218] Without being bound by theory, we envision a combination of components B, C, and D that produces an effective system for stabilizing polyamides at 180°C and higher, while maintaining a completely metal halide-free system. That is, the combination of components B, C, and D provides unexpected stabilization against thermal aging. None of B, C, or D alone is sufficient to produce a stabilizing effect, and components B, C, and D work synergistically.

[0219] In some implementations, the thermoplastic molding compositions are completely free of halogens, and therefore they are also free of halogenated flame retardants.

[0220] Molded articles derived from the above compositions exhibit better heat aging resistance than currently disclosed halogen-based or non-halogen-based stabilizer systems. Thermoplastic parts (such as automotive parts, like cylinder head covers) exposed to extended heat exposure times can achieve longer service lives when manufactured using the disclosed compositions. Furthermore, the improved HAR (Heat Aging Resistance) also allows for the use of such parts at higher temperatures.

[0221] In some embodiments, the thermoplastic molding composition has a tensile strength of at least about 210 MPa at 23°C, such as at least about 210 MPa, at least about 215 MPa, at least about 220 MPa, at least about 225 MPa, etc.

[0222] In some embodiments, the thermoplastic molding composition has a tensile strength of at least about 200 MPa at 23°C after aging at 180°C for 3000 hours, such as at least about 200 MPa, at least about 210 MPa, at least about 215 MPa, at least about 220 MPa, etc.

[0223] In some embodiments, the thermoplastic molding composition retains at least about 50% of its tensile strength after aging at 180°C for 3000 hours, such as at least about 50%, at least about 55%, at least about 60%, at least about 65%, at least about 70%, at least about 75%, at least about 80%, at least about 85%, at least about 90%, at least about 95%, at least about 96%, at least about 97%, at least about 98%, at least about 99%, about 100%, or any value within the range formed by any two of the foregoing values.

[0224] In some embodiments, the thermoplastic molding composition has a tensile strength of at least about 150 MPa at 23°C after aging at 180°C for 5000 hours, such as at least about 150 MPa, at least about 155 MPa, at least about 160 MPa, at least about 165 MPa, at least about 170 MPa, etc.

[0225] In some embodiments, the thermoplastic molding composition retains at least about 40% of its tensile strength after aging at 180°C for 5000 hours, such as at least about 40%, at least about 45%, at least about 50%, at least about 55%, at least about 60%, at least about 65%, at least about 70%, at least about 75%, at least about 80%, at least about 85%, etc.

[0226] Figure 1 This is a graph showing the retention of tensile strength of the disclosed composition after heat aging at 180°C for 5000 hours. Figure 1 As shown, the compositions disclosed herein provide at least about 70% retention of tensile strength after thermal aging.

[0227] In some embodiments, the elongation at break of the thermoplastic molding composition at 23°C is from about 2.0% to about 4.0%. For example, in some embodiments, the elongation at break of the thermoplastic molding composition may be about 2.0%, about 2.1%, about 2.2%, about 2.3%, about 2.4%, about 2.5%, about 2.6%, about 2.7%, about 2.8%, about 2.9%, about 3.0%, about 3.1%, about 3.2%, about 3.3%, about 3.4%, about 3.5%, about 3.6%, about 3.7%, about 3.8%, about 3.9%, about 4.0%, or any value within the range formed by any two of the foregoing values.

[0228] In some embodiments, the elongation at break of the thermoplastic molding composition after heat aging at 180°C for 5000 hours at 23°C is about 1.2% to about 2.5%, such as about 1.2%, about 1.3%, about 1.4%, about 1.5%, about 1.6%, about 1.7%, about 1.8%, about 1.9%, about 2.0%, about 2.1%, about 2.2%, about 2.3%, about 2.4%, about 2.5%, or any value included in the range formed by any two of the foregoing values.

[0229] In some embodiments, the elongation at break of the thermoplastic molding composition after aging at 180°C for 3000 hours retains at least about 50%, such as at least about 50%, at least about 55%, at least about 60%, at least about 65%, at least about 70%, etc.

[0230] In some embodiments, the elongation at break of the thermoplastic molding composition after aging at 180°C for 5000 hours is at least about 40%, such as at least about 40%, at least about 45%, at least about 50%, etc.

[0231] Figure 2 This is a graph showing the retention of tensile elongation after heat aging at 180°C for 5000 hours. (See graph for details.) Figure 2 As shown, the compositions of this disclosure exhibit at least about 50% elongation retention after 3000 hours of heat aging as described herein, and at least about 40% elongation retention after 5000 hours of heat aging as described herein.

[0232] In some embodiments, the notched Izod impact retention of the thermoplastic molding composition after aging at 180°C for 3000 hours is at least about 95%, such as about 95%, about 96%, about 97%, about 98%, about 99%, about 100%, or any value within the range formed by any two of the foregoing values. In some embodiments, the notched Izod impact retention of the thermoplastic molding composition after aging at 180°C for 5000 hours is at least about 90%, such as about 90%, about 91%, about 92%, about 93%, about 94%, about 95%, about 96%, about 97%, about 98%, about 99%, about 100%, or any value within the range formed by any two of the foregoing values.

[0233] Figure 3 This is a graph showing the retention rate of the notched Izod impact strength (NII) of the disclosed composition after heat aging at 180°C for 5000 hours. Figure 3As shown, the compositions disclosed herein exhibit at least about 95% NII retention after 3000 hours of thermal aging as described herein, and at least about 90% NII retention after 5000 hours of thermal aging as described herein.

[0234] Example

[0235] The following thermoplastic molding compositions were prepared as shown in Table 1.

[0236] Table 1

[0237]

[0238] Table 2 shows the tensile properties of the dry-as-molded parts tested at 23°C and the percentage retention of tensile properties after 3000 hours of thermal aging at 180°C. Compared to copper halide-based systems (Composition 1 and Composition 4, respectively), Composition 3 retains 16% to 35% of the additional tensile strength, and compared to Composition 2, it retains 8% of the additional tensile strength.

[0239] Table 2

[0240] Tensile strength (MPa) at 23℃ Tensile strength (MPa) at 23°C after 3000 hours of heat aging in air at 180°C. % retention rate of tensile strength after aging Composition 1 217 168 77 Composition 2 211 179 85 Composition 3 221 206 93 Composition 4 205 118 58

[0241] Table 3 shows the tensile elongation properties of the compositions after heat aging at 180°C for 3000 hours. Compared with copper halide-based systems (compositions 1 and 4, respectively), composition 3 retains an additional 25% to 30% tensile elongation, and compared with composition 2, it retains an additional 18% tensile elongation.

[0242] Table 3

[0243] Elongation at break (%) at 23℃ Elongation at break (%) after 3000 hours of heat aging in air at 180℃ and at 23℃ % retention rate of tensile elongation at break after aging Composition 1 3.5 1.5 43 Composition 2 3.4 1.7 50 Composition 3 3.1 2.1 68 Composition 4 3.2 1.2 38

[0244] Table 4 shows the tensile properties of the dry molding tensile properties tested at 23°C and the percentage retention of tensile properties after the parts have undergone 5000 hours of heat aging at 180°C. Compared with copper halide-based systems (compositions 1 and 4, respectively), composition 3 retains 20% to 49% of the additional tensile strength, and compared with composition 2, it retains 20% of the additional tensile strength.

[0245] Table 4

[0246] Tensile strength (MPa) at 23℃ Tensile strength (MPa) at 23°C after 5000 hours of heat aging in air at 180°C. % retention rate of tensile strength after aging Composition 1 217 118 54 Composition 2 211 114 54 Composition 3 221 163 74 Composition 4 205 51.5 25

[0247] Table 5 shows the tensile elongation properties of the compositions after 5000 hours of heat aging at 180°C. Compared with copper halide-based systems (compositions 1 and 4, respectively), composition 3 retains an additional tensile elongation of 19% to 29%, and compared with composition 2, it retains an additional tensile elongation of 16%.

[0248] Table 5

[0249] Elongation at break (%) at 23℃ Elongation at break (%) after 5000 hours of heat aging in air at 180℃ and at 23℃ % retention rate of tensile elongation at break after aging Composition 1 3.5 1 29 Composition 2 3.4 1.1 32 Composition 3 3.1 1.5 48 Composition 4 3.2 0.62 19

[0250] Table 6 shows the notched Izod impact strength of the compositions after thermal aging at 180°C for 3000 hours. Compared to copper halide-based systems (compositions 1 and 4, respectively), composition 3 retains 27% to 20% additional impact strength, and compared to composition 2, it retains 22% additional impact strength.

[0251] Table 6

[0252] <![CDATA[Izod impact strength at 23°C (KJ / m 2 )]]> <![CDATA[Notched Izod impact strength at 23 °C after 3000 hours of thermal aging in air at 180 °C (KJ / m 2 ).]]> % retention rate of notched Izod impact strength after aging Composition 1 19 15 79 Composition 2 19 16 84 Composition 3 17 18 106 Composition 4 14 12 86

[0253] Table 7 shows the notched Izod impact strength of the compositions after 5000 hours of thermal aging at 180°C. Compared to copper halide-based systems (compositions 1 and 4, respectively), composition 3 retains 38% to 67% of the additional impact strength, and compared to composition 2, it retains 11% of the additional impact strength.

[0254] Table 7

[0255] <![CDATA[Izod impact strength at 23 °C (kJ / m 2 ).]]> <![CDATA[Notched Izod impact strength (KJ / m) at 23 °C after thermal aging in air at 180 °C for 5000 hours 2 > % retention rate of notched Izod impact strength after aging Composition 1 19 13 68 Composition 2 19 18 95 Composition 3 17 18 106 Composition 4 14 5.5 39

[0256] This disclosure is not limited to the specific systems, apparatus, and methods described, as these are subject to change. The terminology used in this specification is for the purpose of describing a particular version or embodiment only and is not intended to be limiting.

[0257] As used herein, unless the context clearly indicates otherwise, the singular forms “a” and “the” include plural indicators. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. Nothing in this disclosure should be construed as an admission that the embodiments described herein are not entitled to prior rights to such disclosure due to prior invention. As used herein, the term “comprising” means “including, but not limited to”.

[0258] As used in this article, the term “about” refers to a number plus or minus 10%. For example, “about 50%” means in the range of 45% to 55%.

[0259] In the detailed description above, reference is made to the accompanying drawings, which form part of that detailed description. In the drawings, like symbols generally identify like parts unless the context otherwise requires. The illustrative embodiments described in the detailed description, drawings, and claims are not intended to be limiting. Other embodiments may be utilized, and other changes may be made, without departing from the spirit or scope of the subject matter presented herein. It will be readily understood that, as generally described herein and shown in the drawings, aspects of this disclosure can be arranged, substituted, combined, separated, and designed in a variety of different configurations, all of which are expressly contemplated herein.

[0260] This disclosure is not limited to the specific embodiments described herein, which are intended to illustrate various aspects. Many modifications and variations may be made to this disclosure without departing from the spirit and scope thereof, as will be apparent to those skilled in the art. In addition to those listed herein, functionally equivalent methods and apparatus within the scope of this disclosure will be apparent to those skilled in the art based on the foregoing description. Such modifications and variations are intended to fall within the scope of the appended claims. This disclosure is limited only by the terms of the appended claims and the full scope of their equivalents. It should be understood that this disclosure is not limited to any particular method, reagent, compound, composition, or biological system, which may of course be varied. It should also be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be restrictive.

[0261] Regarding the use of virtually any plural and / or singular terms in this document, those skilled in the art can convert plural to singular and / or singular to plural as needed by the context and / or application. For clarity, various singular / plural substitutions may be explicitly described herein.

[0262] Those skilled in the art will understand that, generally, the terms used herein and especially in the appended claims (e.g., the body of the appended claims) are intended to be “open” terms (e.g., the term “comprising” should be understood as “including but not limited to,” the term “having” should be understood as “at least having,” the term “including” should be understood as “including but not limited to,” etc.). While various compositions, methods, and apparatuses are described as “comprising” various components or steps (interpreted as meaning “including but not limited to”), compositions, methods, and apparatuses may also be “consistently composed of various components and steps” or “comprises various components and steps,” and such terms should be interpreted as defining a substantially closed group of members. Those skilled in the art will further understand that if a particular number of the introduced claim statements are desired, such an intention will be expressly stated in the claims, and without such a statement, such an intention does not exist.

[0263] For example, to aid understanding, the appended claims may contain the introductory phrases “at least one” and “one or more” to introduce the claim statement. However, the use of such phrases should not be construed as implying that the introduction of the claim statement by the indefinite article “a / an” would limit any particular claim containing such an introduced claim statement to an embodiment containing only one such statement, even when the same claim includes the introductory phrases “one or more” or “at least one” and indefinite articles such as “a” or “an” (e.g., “a” and / or “an” should be interpreted as meaning “at least one” or “one or more”); the same applies to the use of definite articles to introduce the claim statement.

[0264] Furthermore, even when a specific number of introduced claim statements is explicitly stated, those skilled in the art will recognize that such statements should be interpreted as meaning at least the stated number (e.g., in the absence of other modifiers, simply stating "two statements" means at least two statements, or two or more statements). Additionally, in cases where conventions such as "at least one of A, B, and C, etc." are used, generally, such constructions are intended to be understood by those skilled in the art in the sense of the convention (e.g., "a system having at least one of A, B, and C" will include, but is not limited to, systems having a single A, a single B, a single C, A and B together, A and C together, B and C together, and / or A, B, and C together, etc.). In cases where conventions such as "at least one of A, B, or C, etc." are used, generally, such constructions are intended to be understood by those skilled in the art in the sense of the convention (e.g., "a system having at least one of A, B, or C" will include, but is not limited to, systems having a single A, a single B, a single C, A and B together, A and C together, B and C together, and / or A, B, and C together, etc.). Those skilled in the art will further understand that any extractive words and / or phrases that actually represent two or more alternative terms, whether in the specification, claims, or drawings, should be understood to contemplate the possibility of including one, any, or both of the terms. For example, the phrase “A or B” would be understood to include the possibility of “A” or “B” or “A and B”.

[0265] Furthermore, when features or aspects of this disclosure are described in accordance with the Markush Group, those skilled in the art will recognize that this disclosure is also described in accordance with any individual member or subgroup of the Markush Group.

[0266] As those skilled in the art will understand, for any and all purposes, such as in providing a written description, all scopes disclosed herein also encompass any and all possible subscopes and combinations thereof. Any listed scope can be readily identified as sufficiently descriptive and such that the same scope can be decomposed into at least equal halves, thirds, quarters, fifths, tenths, etc. As a non-limiting example, each scope discussed herein can be readily decomposed into a lower third, a middle third, and an upper third, etc. As those skilled in the art will also understand, all language (such as “at most,” “at least,” etc.) includes the listed numbers and refers to scopes that can subsequently be decomposed into subscopes as discussed above. Finally, as those skilled in the art will understand, a scope includes each individual member. Thus, for example, a group having 1 to 3 compounds means a group having 1, 2, or 3 compounds. Similarly, a group having 1 to 5 cells means a group having 1, 2, 3, 4, or 5 compounds, and so on.

[0267] The various features and functions disclosed above, as well as other features and functions, or alternatives thereof, can be combined into many other different systems or applications. Various alternatives, modifications, variations, or improvements that are not currently foreseen or anticipated can then be made by those skilled in the art, each of which is also intended to be covered by the disclosed embodiments.

Claims

1. A thermoplastic molding composition comprising: from about 30 wt% to about 99.9 wt% of at least one thermoplastic polyamide as Component A; from about 0.1 wt. % to about 10 wt. % of at least one polyol as Component B, the polyol having more than six hydroxyl groups and having a number average molecular weight Mn of greater than 2000 g / mol n ; from about 0.05 wt% to about 3 wt% of at least one sterically hindered phenolic antioxidant as Component C; from about 0.1 wt% to about 3 wt% of at least one cationic polyethyleneimine branched polymer as Component D; from 0 wt% to about 50 wt% of at least one fibrous filler and / or particulate filler as Component E; from 0 wt% to about 25 wt% of other additives as Component F; wherein the total wt% of Components A-F is 100 wt%.

2. The thermoplastic molding composition of claim 1, comprising from 45 wt% to 70 wt% of Component A.

3. The thermoplastic molding composition of claim 1, wherein Component A comprises polyamide 6 (PA6), polyamide 66 (PA66), polyamide 12 (PA12), polyamide 610 (PA610), polyamide 46 (PA46), or combinations thereof.

4. The thermoplastic molding composition of claim 1, comprising from 1 wt% to 5 wt% of Component B.

5. The thermoplastic molding composition of claim 1, wherein Component B comprises an ethylene vinyl alcohol copolymer.

6. The thermoplastic molding composition of claim 1, wherein Component C comprises a phenol substituted with one or more of an alkyl group, an alkoxy group, a substituted amino group, or combinations thereof.

7. The thermoplastic molding composition of claim 1, wherein Component C comprises 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionate], pentaerythrityl tetrakis[3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionate], 3,5-di-tert-butyl-4-hydroxybenzylphosphine acid distearyl ester, 3,5-di-tert-butyl-4-hydroxyphenyl-3,5-distearythiopropionitrile, 2-(2'-hydroxy-3',5'-di-tert- butylphenyl)-5-chlorobenzotriazole, 2,6-di-tert-butyl-4-hydroxymethylphenol, 1,3,5-trimethyl- 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 4,4'-methylenebis(2,6-di-tert-butylphenol), 3,5-di-tert-butyl-4-hydroxybenzyl dimethylamine, N,N'-hexamethylenebis-3,5-di-tert-butyl-4- hydroxycinnamamide, or combinations thereof.

8. The thermoplastic molding composition of claim 1, comprising from 0.1 wt% to 1.5 wt% of Component D.

9. The thermoplastic molding composition according to claim 1, wherein component D has a number average molecular weight Mn of more than 1000 g / mol n .

10. The thermoplastic molding composition according to claim 1, wherein component D has a number average molecular weight Mnof about 1300 g / mol n .

11. The thermoplastic molding composition of claim 1, wherein Component D has a cationic charge density of about 16 meq / g DS.

12. The thermoplastic molding composition of claim 1, comprising 10 to 50 weight percent of Component E.

13. The thermoplastic molding composition of claim 1, wherein Component E comprises carbon fibers, glass fibers, glass beads, amorphous silica, calcium silicate, calcium metasilicate, magnesium carbonate, kaolin, chalk, powdered quartz, mica, barium sulfate, feldspar, aramid fibers, potassium titanate fibers, kaolin, calcined kaolin, wollastonite, talc, chalk, layered nanofillers, acicular nanofillers, boehmite, bentonite, montmorillonite, vermiculite, hectorite, synthetic laponite, or combinations thereof.

14. The thermoplastic molding composition of claim 1, wherein the thermoplastic molding composition has a tensile strength retention of at least about 85% after aging at 180 °C for 3000 hours.

15. The thermoplastic molding composition of claim 1, wherein the thermoplastic molding composition has a tensile strength retention of at least about 90% after aging at 180 °C for 3000 hours.

16. The thermoplastic molding composition of claim 1, wherein the thermoplastic molding composition has a tensile strength retention of at least about 60% after aging at 180 °C for 5000 hours.

17. The thermoplastic molding composition of claim 1, wherein the thermoplastic molding composition has a tensile strength retention of at least about 70% after aging at 180 °C for 5000 hours.

18. The thermoplastic molding composition of claim 1, wherein the thermoplastic molding composition has a tensile elongation at break retention of at least about 55% after aging at 180 °C for 3000 hours.

19. The thermoplastic molding composition of claim 1, wherein the thermoplastic molding composition has a tensile elongation at break retention of at least about 65% after aging at 180 °C for 3000 hours.

20. The thermoplastic molding composition of claim 1, wherein the thermoplastic molding composition has a tensile elongation at break retention of at least about 40% after aging at 180 °C for 5000 hours.

21. The thermoplastic molding composition of claim 1, wherein the thermoplastic molding composition has a notched Izod impact strength retention of at least about 95% after aging at 180 °C for 3000 hours.

22. The thermoplastic molding composition of claim 1, wherein the thermoplastic molding composition has a notched Izod impact strength retention of at least about 90% after aging at 180 °C for 5000 hours.

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