Polyamide molding compositions with improved heat-aging resistance

Abstract

The present disclosure describes thermoplastic molding compositions which may include about 30 wt. % to about 99.9 wt. % of at least one thermoplastic polyamide as component A; about 0.1 wt. % to about 10 wt. % of at least one polyhydric alcohol having more than six hydroxyl groups and having a number average molecular weight Mn of greater than 2000 g / mol as component B; about 0.05 wt. % to about 3 wt. % of at least one sterically hindered phenol 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 and / or particulate filler as component E; 0 to about 25 wt. % of further additives as component F; wherein the total wt. % of components A through F is 100 wt. %.

Description

POLYAMIDE MOLDING COMPOSITIONS WITH IMPROVED HEAT-AGINGRESISTANCECROSS-REFERENCE 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 content of which is incorporated by reference herein in its entirety.BACKGROUND

[0002] Thermoplastic polyamides, such as PA6 and PA66, are often used in the form of glass fiber-reinforced molding compositions as materials in the design of components which during their lifetime have exposure to elevated temperatures and / or humidity with thermo-oxidative degradation.

[0003] Different heat-aging resistant additives which counteract or delay thermo-oxidative degradation are used in polyamide molding compositions, for example, a combination of Cu- containing stabilizers, organic HALS (hindered amine light stabilizers) compounds or sterically hindered phenols or polyhydroxy alcohols. It is highly desirable to improve the heat-aging resistance (HAR) of polyamides since this can achieve longer lifetimes for components subject to thermal stress or can reduce the risk for structural failure. Additionally, improved HAR can also permit the use of the components at higher temperatures.

[0004] The heat-aging resistance of the known molding compositions remains unsatisfactory, in particular over prolonged periods of exposure to heat. In addition, due to increasing electrification more and more applications require materials to be free of any halide-based stabilizer systems (e.g., copper iodide) due the risk of corrosion and respective failures. Therefore, none of the compositions disclosed in the quoted literature fulfills a combination of good thermal stability while avoiding the application of the widely used metal-halide stabilizers.

[0005] Thermoplastic molding compositions without metal halide stabilizers have been previously investigated (such as in U.S. Patent Application Publication No. 2023 / 0128646, whichis incorporated herein in its entirety); however, there remains a need for metal-halide-free thermoplastic molding compositions with improved tensile and impact property retention.SUMMARY

[0006] In some aspects, the techniques described herein relate to a thermoplastic molding composition, including: about 30 wt. % to about 99.9 wt. % of at least one thermoplastic polyamide as component A; about 0.1 wt. % to about 10 wt. % of at least one polyhydric alcohol having more than six hydroxyl groups and having a number average molecular weight Mnof greater than 2000 g / mol as component B; about 0.05 wt. % to about 3 wt. % of at least one sterically hindered phenol antioxidant as component C; about 0.1 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 and / or particulate filler as component E; 0 to about 25 wt. % of further additives as component F; wherein the total wt. % of components A through F is 100 wt. %.

[0007] In some aspects, the techniques described herein relate to a thermoplastic molding composition, including about 45 wt. % to about 70 wt. % of component A.

[0008] In some aspects, the techniques described herein relate to a thermoplastic molding composition, wherein component A includes polyamide 6 (PA6), polyamide 66 (PA66), polyamide 12 (PA 12), polyamide 610 (PA610), polyamide 46 (PA46), or combinations thereof.

[0009] In some aspects, the techniques described herein relate to a thermoplastic molding composition, including about 1 wt. % to about 5 wt. % of component B.

[0010] In some aspects, the techniques described herein relate to a thermoplastic molding composition, wherein component B includes an ethylene vinyl alcohol copolymer.

[0011] In some aspects, the techniques described herein relate to a thermoplastic molding composition, wherein component C includes a phenol substituted with one or more of an alkyl group, an alkoxy group, a substituted amino group, or combinations thereof.

[0012] In some aspects, the techniques described herein relate to a thermoplastic molding composition, wherein component C includes 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 1,6- hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], distearyl 3,5-di-tert-butyl-4- hydroxybenzylphosphonate, 2,6,7-trioxa-l-phosphabicyclo[2.2.2]oct-4-ylmethyl 3,5-di-tert- butyl-4-hydroxyhydrocinnamate, 3,5-ditert-butyl-4-hydroxyphenyl-3,5-distearylthiotriazylamine, 2-(2'-hydroxy-3'-hydroxy-3',5'-di-tertbutylphenyl)-5-chlorobenzotriazole, 2,6-di-tert-butyl-4- hydroxymethylphenol, l,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-hydroxyhydrocinnamide, or combinations thereof.

[0013] In some aspects, the techniques described herein relate to a thermoplastic molding composition, including about 0.1 wt. % to about 1.5 wt. % of component D.

[0014] In some aspects, the techniques described herein relate to a thermoplastic molding composition, wherein component D has a number average molecular weight Mn of greater than about 1000 g / mol.

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

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

[0017] In some aspects, the techniques described herein relate to a thermoplastic molding composition, including about 10 wt. % to about 50 wt. % of component E.

[0018] In some aspects, the techniques described herein relate to a thermoplastic molding composition, wherein 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, aramid fibers, potassium titanate fibers, kaolin, calcined kaolin, wollastonite, talc, chalk, lamellar nanofillers, acicular nanofillers, boehmite, bentonite, montmorillonite, vermiculite, hectorite, laponite, or combinations thereof.

[0019] In some aspects, the techniques described herein relate to a thermoplastic molding composition, wherein the thermoplastic molding composition has a tensile strength retention of at least about 85% after aging for 3000 hours at 180 °C.

[0020] In some aspects, the techniques described herein relate to a thermoplastic molding composition, wherein the thermoplastic molding composition has a tensile strength retention of at least about 90% after aging for 3000 hours at 180 °C.

[0021] In some aspects, the techniques described herein relate to a thermoplastic molding composition, wherein the thermoplastic molding composition has a tensile strength retention of at least about 60% after aging for 5000 hours at 180 °C.

[0022] In some aspects, the techniques described herein relate to a thermoplastic molding composition, wherein the thermoplastic molding composition has a tensile strength retention of at least about 70% after aging for 5000 hours at 180 °C.

[0023] In some aspects, the techniques described herein relate to a thermoplastic molding composition, wherein the thermoplastic molding composition has a tensile elongation at break retention of at least about 55% after aging for 3000 hours at 180 °C.

[0024] In some aspects, the techniques described herein relate to a thermoplastic molding composition, wherein the thermoplastic molding composition has a tensile elongation at break retention of at least about 65% after aging for 3000 hours at 180 °C.

[0025] In some aspects, the techniques described herein relate to a thermoplastic molding composition, wherein the thermoplastic molding composition has a tensile elongation at break retention of at least about 40% after aging for 5000 hours at 180 °C.

[0026] In some aspects, the techniques described herein relate to a thermoplastic molding composition, wherein the thermoplastic molding composition has a notched Izod impact strength retention of at least about 95% after aging for 3000 hours at 180 °C.

[0027] In some aspects, the techniques described herein relate to a thermoplastic molding composition, wherein the thermoplastic molding composition has a notched Izod impact strength retention of at least about 90% after aging for 5000 hours at 180 °C.DRAWINGS

[0028] Aspects, features, benefits, and advantages of the embodiments described herein will be apparent with regard to the following description, appended claims, and accompanying drawings where:

[0029] FIG. 1 is graph of retention of tensile strength of the compositions of the present disclosure after heat aging at 180 °C over a time of 5000 hours.

[0030] FIG. 2 is graph of retention of tensile elongation of the compositions of the present disclosure after heat aging at 180 °C over a time of 5000 hours.

[0031] FIG. 3 is graph of retention of notched Izod impact of the compositions of the present disclosure after heat aging at 180 °C over a time of 5000 hoursDETAILED DESCRIPTION

[0032] The present disclosure describes thermoplastic molding compositions including polyamides which have improved heat-aging resistance (HAR), and which, after heat-aging, retain good mechanical properties. The components disclosed herein can act as a heat stabilizer in thermoplastic polyamide molding compositions, and significantly improve the heat-aging resistance over prolonged periods of exposure to heat.

[0033] In some embodiments, there is provided a thermoplastic molding composition, including: about 30 wt. % to about 99.9 wt. % of at least one thermoplastic polyamide as component A; about 0.1 wt. % to about 10 wt. % of at least one polyhydric alcohol having more than six hydroxyl groups and having a number average molecular weight Mn of greater than 2000 g / mol as component B; about 0.05 wt. % to about 3 wt. % of at least one sterically hindered phenol antioxidant as component C; about 0.1 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 and / or particulate filler as component E; 0 to about 25 wt. % of further additives as component F; wherein the total wt. % of components A through F is 100 wt. %.

[0034] As disclosed herein, the number average molecular weight as well as the weight average molecular weight (Mn, Mw, respectively) and polydispersity data can be obtained using gel permeation chromatography (GPC) in hexafluoroisopropanol as solvent with PMMAcalibration. This molecular weight determination can be employed for all components of the thermoplastic molding compositions according to the present invention.

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

[0036] If components E or F, or combinations thereof are present in the thermoplastic molding composition, the maximum amount of component A is decreased by the minimum amount of each of component E or F, or a combination thereof, such that the total wt. % of components A through F is 100 wt. %.

[0037] The polyamides of the molding compositions of the invention generally have an intrinsic viscosity of from 90 to 350 ml / g, preferably from 110 to 240 ml / g, determined in a 0.5% strength by weight solution in 96% strength by weight sulfuric acid at 25 °C to ISO 307.

[0038] Particularly contemplated are semicrystalline or amorphous resins with a molecular weight (weight average) of at least 5000, described by way of example in the following US patents: U.S. Patent No. 2,071,250, U.S. Patent No. 2,071,251, U.S. Patent No. 2,130,523, U.S. Patent No. 2,130,948, U.S. Patent No. 2,241,322, U.S. Patent No. 2,312,966, U.S. Patent No. 2,512,606, and U.S. Patent No. 3,393,210.

[0039] Examples of these are polyamides that derive from lactams having from 7 to 13 ring members, such as polycaprolactam, polycaprylolactam, and polylaurolactam, and also polyamides obtained via reaction of dicarboxylic acids with diamines.

[0040] Dicarboxylic acids which may be used are alkanedicarboxylic acids having from 6 to 12, in particular from 6 to 10 carbon atoms, and aromatic dicarboxylic acids. Merely as examples, those that may be mentioned here are adipic acid, azelaic acid, sebacic acid, dodecanedioic acid and terephthalic and / or isophthalic acid.

[0041] Particularly suitable diamines are alkanediamines having from 6 to 12, in particular from 6 to 8, carbon atoms, and also m-xylylenediamine, di(4-aminophenyl)methane, di(4- aminocyclohexyl)methane, 2,2-di(4-aminophenyl)propane, 2,2-di(4-aminocyclohexyl)propane, and l,5-diamino-2-methylpentane.

[0042] In some embodiments, preferred polyamides include polyhexamethyleneadipamide, polyhexamethylenesebacamide, and polycaprolactam, and also nylon-6 / 6, 6 copolyamides, in particular having a proportion of from 5 to 95 wt % of caprolactam units (e.g. Ultramid® C31 from BASF SE).

[0043] Other suitable polyamides are obtainable from co-aminoalkylnitriles, such as aminocapronitrile (PA 6) and adipodinitrile with hexamethylenediamine (PA 66) via what is known as direct polymerization in the presence of water, for example as described in DE-A 10313681, EP-A 1198491 and EP 922065.

[0044] Mention may also be made of polyamides obtainable, by way of example, via condensation of 1,4-diaminobutane with adipic acid at an elevated temperature (nylon-4, 6). Preparation processes for polyamides of this structure are described by way of example in EP-A 38094, EP-A 38582, and EP-A 39524.

[0045] Other suitable examples are polyamides obtainable via copolymerization of two or more of the abovementioned monomers, and mixtures of two or more polyamides in any desired mixing ratio. Particular preference is given to mixtures of nylon-6, 6 with other polyamides, in particular blends of nylon-6 and nylon-66, and to nylon-6 / 6, 6 copolyamides and nylon-6, 6 / 6 copolyamides.

[0046] Other copolyamides which have proven particularly advantageous are semiaromatic copolyamides, such as PA 6 / 6T and PA 66 / 6T, where the triamine content of these is less than 0.5 wt %, preferably less than 0.3 wt % (see EP-A 299444). Other polyamides resistant to high temperatures are known from EP-A 1994075 (PA 6T / 61 / MXD6).

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

[0048] The following list, which is not comprehensive, includes the polyamides A) mentioned and other polyamides A) for the purposes of the present disclosure, and the monomers including:

[0049] AB polymers:

[0050] PA 4 Pyrrolidone

[0051] PA 6 ε-Caprolactam

[0052] PA 7 Ethanolactam

[0053] PA 8 Caprylolactam

[0054] PA 99-Aminopelargonic acid

[0055] PA 11 11-Aminoundecanoic acid

[0056] PA 12 Laurolactam

[0057] AA / BB polymers:

[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-Xylylenediamine, adipic acid

[0068] AA / BB polymers:

[0069] PA 61 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 61 and PA 6T)

[0076] PA PACM 12 Diaminodicyclohexylmethane, laurolactam

[0077] PA 6I / 6T / PACM as PA 61 / 6T+diaminodicyclohexylmethane

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

[0079] PA 12 / MACMT Lauro lactam, dimethyldiaminodicyclohexylmethane, terephthalic acid

[0080] PA PDA-T Phenylenediamine, terephthalic acid

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

[0082] Suitable copolyamides may be constructed from:

[0083] Al) 20.0 to 90.0 wt % of units derived from terephthalic acid and hexamethylenediamine,

[0084] A2) 0 to 50.0 wt % of units derived from e-caprolactam,

[0085] A3) 0 to 80.0 wt % of units derived from adipic acid and hexamethylenediamine,

[0086] A4) 0 to 40.0 wt % of further polyamide-forming monomers,

[0087] wherein the proportion of component A2) or A3) or A4), or mixtures thereof is at least10.0 wt %.

[0088] Component Al) includes 20.0 to 90.0 wt % of units derived from terephthalic acid and hexamethylenediamine.

[0089] In addition to the units derived from terephthalic acid and hexamethylenediamine, the copolyamides optionally include units derived from ε-caprolactam and / or units derived from adipic acid and hexamethylenediamine and / or units derived from further polyamide-forming monomers.

[0090] Aromatic dicarboxylic acids A4) include 8 to 16 carbon atoms. Suitable aromatic dicarboxylic acids include, for example, isophthalic acid, substituted terephthalic and isophthalic acids, such as 3-t-butylisophthalic acid, polycyclic dicarboxylic acids, for example 4,4'- and 3,3'- diphenyldicarboxylic acid, 4,4'- and 3, 3 '-diphenylmethanedicarboxylic acid, 4,4'- and 3,3'- sulfodiphenylcarboxylic acid, 1,4- or 2,6-naphthalenedicarboxylic acid, phenoxyterephthalic acid, isophthalic acid being particularly preferred.

[0091] Further polyamide-forming monomers A4) may be derived from dicarboxylic acids having 4 to 16 carbon atoms and aliphatic or cycloaliphatic diamines having 4 to 16 carbon atoms, and also from aminocarboxylic acids / corresponding lactams having 7 to 12 carbon atoms. Examples of suitable monomers of these types mention are suberic 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 meta-xylylenediamine as representatives of diamines and caprolactam, enantholactam, ω -aminoundecanoic acid and laurolactam as representatives of lactams / aminocarboxylic acids. Suitable such copolyamides are more particularly elucidated in DE- A- 102009011668.

[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 includes about 0.1 wt. % to about 10 wt. % of at least one polyhydric alcohol having more than six hydroxyl groups and having a number average molecular weight Mnof greater than 2000 g / mol as component B. For example, the thermoplastic molding composition may include component B in an amount 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 value contained within a range formed by any two of the preceding values.

[0094] In some embodiments, Component B includes at least one polyhydric alcohol having more than 6 hydroxyl groups and having a number average molecular weight Mnof more than 2000 g / mol. Component B may have more than 8, or more than 10 hydroxyl groups.

[0095] Component B in some embodiments has a number average molecular weight Mnof more than 3000 g / mol, such as more than 5000 g / mol, or more than 10000 g / mol. The maximum number average molecular weight preferably is 35000 g / mol, more preferably 25000 g / mol. A specifically preferred component B has a number average molecular weight of from 10000 to 30000 g / mol, more preferably 12500 to 22500 g / mol, most preferably 15000 to 20000 g / mol.

[0096] The weight average Mwis preferably from 10000 to 250000 g / mol, more preferably 25000 to 120000 g / mol, in particular 30000 to 80000 g / mol.

[0097] Component B can be selected from all suitable polyhydric alcohols, as long as they have more than 6 hydroxyl groups and have a number average molecular weight Mnof more than 2000 g / mol. Examples of suitable polyhydric alcohols are ethylene-vinyl alcohol copolymers are commercially available by Mitsubishi Chemical under the trade name Soamol™ or by Kuraray under the tradename EVAL™. In some embodiments, other high molecular weight polyhydric alcohols may be suitable as well.

[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 from 10 to 60 mol %, more preferably 20 to 50 mol %, in particular 25 to 50 mol %.

[0099] Besides ethylene and vinyl alcohol, residual amounts of vinyl acetate can be present in the copolymer, preferably 20 mol % or less, more preferably 10 mol % or less, in particular 5 mol % or less. Most preferably there are no residual amounts of vinylacetate. The ethylene-vinyl alcohol copolymer can be obtained by partial or complete hydrolysis of ethylene-vinyl acetate copolymers.

[0100] An especially suitable ethylene-vinyl alcohol copolymer has a number average molecular weight Mnof from 10000 to 30000 g / mol, more preferably 12500 to 22500 g / mol, most preferably 15000 to 20000 g / mol. Most preferred, it has a number average molecular weight Mn of 18000 g / mol, and a weight average molecular weight Mw of 50000 g / mol.

[0101] The polyhydric alcohol can also contain additional functional groups that are not hydroxyl groups. Preferably, however, the polyhydric alcohol contains only hydroxyl groups as functional groups. The polyhydric alcohol can be linear, branched or hyperbranched. Specifically, highly branched or hyper branched structures partially consisting of hydroxy-functional groups as described in EP 2227507 Bl and DE 102004051241 Al are also suitable to achieve the desired effect. For example, highly branched or hyperbranched polyetheramines having a hydroxyl number of from 50 to 1000 mg KOH / g, preferably 100 to 900 mg KOH / g, more preferably 150 to 800 mg KOH / g can be employed.

[0102] In some embodiments, the thermoplastic molding composition includes about 0.05 wt. % to about 3 wt. % of at least one sterically hindered phenol antioxidant as component C. For example, the thermoplastic molding composition may include component C in an amount of 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 value contained within a range formed by any two of the preceding values.

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

[0104] Component C has preferably at least one, more preferably at least two phenol groups substituted by at least one branched C3- 12 -alkyl group as a sterically hindering group. The substituted phenol groups are covalently linked with the structure of component C.

[0105] Suitable sterically hindered phenols for use as component C are, in principle, all of the compounds which have a phenolic structure, and which have at least one bulky group on the phenolic ring. A bulky group is for example a branched C3-12-alkyl group, preferably a branched C3-6-alkyl group, more preferably an isopropyl or tert-butyl group.

[0106] It is in some embodiments preferable to use, for example, compounds of the formula:

[0107] wherein R1and R2are each an alkyl group, a substituted alkyl group, or a substituted triazole group, and where the radicals R1and R2may be identical or different, and R3is an alkyl group, a substituted alkyl group, an alkoxy group, or a substituted amino group. The alkyl and alkoxy residues have preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms. Substituents are preferably C1-12-alkyl, more preferably C1-6-alkyl, most preferably C1-4-alkyl. At least one of R1to R3is preferably a bulky group as defined above.

[0108] Antioxidants of the abovementioned type are described by way of example in DE-A 2702661 (U.S. Pat. No. 4,360,617).

[0109] Another group of preferred sterically hindered phenols is provided by those derived from substituted phenylcarboxylic acids, in particular from substituted phenylpropionic acids, which preferably have at least one bulky group on the phenyl group. They contain at least one, preferably two covalently linked substituted phenylcarboxylic acid unit(s) in their structure, which preferably have at least one bulky group on the phenyl group.

[0110] Preferred phenylcarboxylic acids are phenyl-C1-12-carboxylic acids, more preferably phenyl-C2-6-carboxylic acids. The phenyl group is preferably a phenol group having at least one bulky group on the phenolic ring, as indicated above. Thus, the above-mentioned sterically hindered phenols are preferably covalently linked with a C1-12-alkane carboxylic acid, more preferably a linear C2-6-alkane carboxylic acid.

[0111] Particularly preferred compounds from this class are compounds of the formula:

[0112] wherein R4, R5, R7, and R8, independently of one another, are C1-C8-alkyl groups which themselves may have substitution (at least one of these being a bulky group), and R6is a divalent aliphatic radical which has from 1 to 10 carbon atoms and whose main chain may also have C — O bonds. At least one of R4to R8is a bulky group as defined above.

[0113] Preferred compounds corresponding to these formulae are:

[0115] (Irganox® 259 from BASF SE)

[0116] All of the following should be mentioned as examples of sterically hindered phenols which may be included in the compositions of the present disclosure as component C:

[0117] 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] (Irganox® 1010 from BASF SE), distearyl 3,5-di-tert-butyl-4- hydroxybenzylphosphonate, 2,6,7-trioxa-l-phosphabicyclo[2.2.2]oct-4-ylmethyl 3,5-di-tert- butyl-4-hydroxyhydrocinnamate, 3,5-ditert-butyl-4-hydroxyphenyl-3,5-distearylthiotriazylamine, 2-(2’-hydroxy-3'-hydroxy-3',5’-di-tertbutylphenyl)-5-chlorobenzotriazole, 2,6-di-tert-butyl-4- hydroxymethylphenol, l,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, or combinations thereof.

[0118] Compounds which have proven particularly effective, without wishing to be bound by theory, and which are therefore used with preference are 2,2'-methylenebis(4-methyl-6-tert- butylphenol), 1,6-hexanediol bis(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (Irganox® 259), pentaerythrityl tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and also N,N’- hexamethylenebis-3,5-di-tert-butyl-4-hydroxyhydrocinnamide (Irganox® 1098), and the products Irganox® 245 and Irganox® 1010 described above from BASF SE, which have particularly good suitability.

[0119] In some embodiments, sterically hindered phenols having not more than one sterically hindered group in ortho-position with respect to the phenolic hydroxy group have proven particularly advantageous; in particular when assessing colorfastness on storage in diffuse light over prolonged periods.

[0120] In some embodiments, the thermoplastic molding composition includes 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 include component D in an amount of 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 value contained within a range formed by any two of the preceding values.

[0121] In some embodiments, component D has a number average molecular weight Mnof 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 a range formed by any two of the preceding values.

[0122] In some embodiments, component D has a cationic charge density of 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 a range formed by any two of the preceding values.

[0123] In some embodiments, polyethylenimines can be selected from highly branched polyethylenimines. Highly branched polyethylenimines are characterized by their high degree of branching (DB). The degree of branching can be determined, for example, by13C-NMR spectroscopy, preferably in D2O, and is defined as follows:

[0124] DB=D+T / D+T+L

[0125] with D (dendritic) corresponding to the fraction of tertiary amino groups, L (linear) corresponding to the fraction of secondary amino groups and T (terminal) corresponding to the fraction of primary amino groups.

[0126] Within the context of the present disclosure, highly branched polyethylenimines are polyethylenimines with DB in the range from 0.25 to 0.90.

[0127] In some embodiments, polyethylenimines are selected from copolymers of ethylenimine, such as copolymers of ethylenimine with at least one diamine with two NH2 groups per molecule other than ethylenimine, for example propylene imine, or with at least one compound with three NH2 groups per molecule such as melamine.

[0128] Suitable compounds which may be used as component D include but are not limited to Lupasol® G 20 WF from BASF.

[0129] Without wishing to be bound by theory, component B and component D can, in some embodiments, induce a synergistic effect which allows high performance and strong retention oftensile strength, tensile elongation, and notched Izod impact in the compositions of the present disclosure. In some embodiments, the compositions of the present disclosure, which include both component B and component D, achieve improved performance relative to compositions which include only one of component B or component D.

[0130] In some embodiments, the thermoplastic molding composition includes 0 wt. % to about 50 wt. % of at least one fibrous and / or particulate filler as component E. In some embodiments, the thermoplastic molding composition includes 0 wt. % of component E, such that component E is omitted. In other embodiments, the thermoplastic molding composition includes component E in an amount of about 1 wt. %, about 5 wt. %, about 10 wt. %, about 15 wt. %, about 20 wt. %, about 25 wt. %, about 30 wt. %, about 35 wt. %, about 40 wt. %, about 45 wt. %, about 50 wt. %, or any value contained within a range formed by any two of the preceding values.

[0131] 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 fibrous fillers that may be mentioned are carbon fibers, aramid fibers, and potassium titanate fibers, particular preference being given to glass fibers in the form of E glass. These can be used as rovings or in the commercially available forms of chopped glass.

[0132] The fibrous fillers may have been surface-pretreated with a silane compound to improve compatibility with the thermoplastic. Suitable silane compounds have the general formula:

[0133] (X — (CH2)n)k — Si — (O - CmH2m+1)4-k

[0134] where the definitions of the substituents are as follows:

[0135] X - NH2, epoxide, or OH,

[0136] n is a whole number from 2 to 10, preferably 3 to 4,

[0137] m is a whole number from 1 to 5, preferably 1 to 2, and

[0138] k is a whole number from 1 to 3, preferably 1.

[0139] Preferred silane compounds are aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane and aminobutyltri ethoxysilane, and also the corresponding silanes which comprise a glycidyl group as substituent X.

[0140] The amounts of the silane compounds generally used for surface-coating are from 0.01 wt. % to 2 wt. %, preferably from 0.025 wt. % to 1.0 wt. % and in particular from 0.05 wt. % to 0.5 wt. % (based on the weight of component E).

[0141] Acicular mineral fillers are also suitable. For the purposes of the invention, acicular mineral fillers are mineral fillers with strongly developed acicular character. An example is acicular wollastonite. The mineral preferably has an L / D (length to diameter) ratio of from 8:1 to 35:1 , preferably from 8: 1 to 11: 1. The mineral filler may optionally have been pretreated with the abovementioned silane compounds, but the pretreatment is not essential.

[0142] Other fillers which may be mentioned are kaolin, calcined kaolin, wollastonite, talc and chalk, and also lamellar or acicular nanofillers, the amounts of these preferably being from 0.1 to 10%. Materials preferred for this purpose are boehmite, bentonite, montmorillonite, vermiculite, hectorite, and laponite. The lamellar nanofillers are organically modified by prior art methods, to give them good compatibility with the organic binder. Addition of the lamellar or acicular nanofillers to the inventive nanocomposites gives a further increase in mechanical strength.

[0143] In some embodiments, the thermoplastic molding composition includes 0 to about 25 wt. % of further additives as component F. For example, in some embodiments, the thermoplastic molding composition may include 0 wt. % of component F, such that component F is omitted, or may include component F in an amount of about 1 v / t. about 5 wt. %, about 10 wt. %, about 15 wt. %, about 20 wt. %, about 25 wt. %, or any value contained within a range formed by any two of the preceding values.

[0144] If further additives are employed, the minimum amount is preferably 0.1 wt %, more preferably 0.25 wt %, most preferably 0.5 wt %.

[0145] The thermoplastic molding compositions of the invention can include as component F conventional processing aids, further stabilizers, oxidation retarders, agents to counteractdecomposition by heat and decomposition by ultraviolet light, lubricants and mold-release agents, colorants, such as dyes and pigments, nucleating agents, plasticizers, etc.

[0146] The thermoplastic molding compositions of the present disclosure can include, as component F, from about 0.05 to about 3% by weight, preferably from about 0.1 to about 1.5% by weight, and in particular from about 0.1 to about 1% by weight, of a lubricant.

[0147] Preference is given to the salts of aluminum, of alkali metals, or of alkaline earth metals, or esters or amides of fatty acids having from 10 to 44 carbon atoms, preferably having from 12 to 44 carbon atoms. The metal ions are preferably alkaline earth metal and aluminum, particular preference being given to calcium or magnesium.

[0148] Preferred metal salts include calcium stearate and calcium montanate, and also aluminum stearate. It is also possible to use a mixture of various salts, in any desired mixing ratio.

[0149] In some embodiments, the molding compositions of the invention can include, as component F, from about 0.05 to about 3% by weight, preferably from about 0.1 to about 1.5% by weight, and in particular from about 0.1 to about 1% by weight, of a copper stabilizer, preferably of a Cu(I) halide, in particular in a mixture with an alkali metal halide, preferably KI, in particular in the ratio 1 :4, or of a sterically hindered phenol, or a mixture of these.

[0150] In some embodiments, the carboxylic acids disclosed herein can be monobasic or dibasic. Examples which may be mentioned are pelargonic acid, palmitic acid, lauric acid, margaric acid, dodecanedioic acid, behenic acid, and particularly preferably stearic acid, capric acid, and also montanic acid (a mixture of fatty acids having from 30 to 40 carbon atoms).

[0151] In some embodiments, the aliphatic alcohols disclosed herein can be monohydric to tetrahydric. Examples of alcohols are n-butanol, n-octanol, stearyl alcohol, ethylene glycol, propylene glycol, neopentyl glycol, pentaerythritol, preference being given to glycerol and pentaerythritol.

[0152] In some embodiments, the aliphatic amines disclosed herein can be mono- to tribasic. Examples of these are stearylamine, ethylenediamine, propylenediamine, hexamethylenediamine, di(6-aminohexyl)amine, particular preference being given to ethylenediamine andhexamethylenediamine. Preferred esters or amides are correspondingly glycerol distearate, glycerol tristearate, ethylenediamine distearate, glycerol monopalmitate, glycerol trilaurate, glycerol monobehenate, and pentaerythritol tetrastearate.

[0153] It is also possible to use a mixture of various esters or amides, or of esters with amides in combination, in any desired mixing ratio.

[0154] According to a preferred embodiment of the present invention, the molding compositions are free from copper, specifically from copper stabilizers, such as Cu / (I)halides, and combinations of Cu(I) halides with alkali metal halides.

[0155] More preferably, the thermoplastic molding compositions of the present inventions are metal halide-free. Metal halide-free systems, so-called electro-friendly systems, are of high interest, since electro-mobility, electrification and connectivity are an increasing trend in almost all industries. Therefore, in some embodiments, the thermoplastic molding composition is preferably free from metal halides, specifically copper halides and alkali metal halides. In some embodiments, the metal halide is present at a very low amount. For example, the metal halide may be present from about 0.001% to about 1 % by weight

[0156] Examples of other conventional additives F are amounts of up to about 25 wt. %, preferably up to about 20 wt. % of elastomeric polymers (also often termed impact modifiers, elastomers, or rubbers).

[0157] The elastomeric polymers disclosed herein with respect to component F are different from component D if component D is employed in the molding compositions according to the present invention. Therefore, in the case that the compositions contain component D, the polymers of component F, especially the elastomeric polymers, are different from the polymers of component D. Likewise, the polymers of components F are different from the polymers of component B.

[0158] These are very generally copolymers preferably composed of at least two of the following monomers: ethylene, propylene, butadiene, isobutene, isoprene, chloroprene, vinyl acetate, styrene, acrylonitrile and acrylates and / or methacrylates having from 1 to 18 carbon atoms in the alcohol component.

[0159] Polymers of this type are described, for example, in Houben-Weyl, Methoden der organischen Chemie, vol. 14 / 1 (Georg-Thieme- Verlag, Stuttgart, Germany, 1961), pages 392 to 406, and in the monograph by C. B. Bucknail, Toughened Plastics (Applied Science Publishers, London, U K, 1977).

[0160] Preferred types of such elastomers are those known as ethylene-propylene (EPM) and ethylene-propylene-diene (EPDM) rubbers. EPM rubbers generally have practically no residual double bonds, whereas EPDM rubbers may have from 1 to 20 double bonds per 100 carbon atoms.

[0161] Examples which may be mentioned of diene monomers for EPDM rubbers are conjugated dienes, such as isoprene and butadiene, non-conjugated dienes having from 5 to 25 carbon atoms, such as 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 2,5-dimethyl-l,5-hexadiene and 1,4-octadiene, cyclic dienes, such as cyclopentadiene, cyclohexadienes, cyclooctadienes and dicyclopentadiene, and also alkenylnorbomenes, such as 5-ethylidene-2-norbomene, 5- butylidene-2-norbomene, 2-methallyl-5-norbomene and 2-isopropenyl-5-norbomene, and tricycledienes, such as 3-methyltricyclo[5.2.1.02,6]-3,8-decadiene, and mixtures of these. Preference is given to 1,5-hexadiene, 5-ethylidenenorbomene and dicyclopentadiene. The diene content of the EPDM rubbers is preferably from 0.5 to 50 wt %, in particular from 1 to 8 wt %, based on the total weight of the rubber.

[0162] EPM rubbers and EPDM rubbers may preferably also have been grafted with reactive carboxylic acids or with derivatives of these. Examples of these are acrylic acid, methacrylic acid and derivatives thereof, such as glycidyl (meth)acrylate, and also maleic anhydride.

[0163] Copolymers of ethylene with acrylic acid and / or methacrylic acid and / or with the esters of these acids are another group of preferred rubbers. The rubbers may also comprise dicarboxylic acids, such as maleic acid and fumaric acid, or derivatives of these acids, such as esters and anhydrides, and / or monomers comprising epoxy groups. These dicarboxylic acid derivatives or monomers comprising epoxy groups are preferably incorporated into the rubber by adding to the monomer mixture monomers comprising dicarboxylic acid groups and / or epoxy groups and having the general formulae I or II or III or IV:

[0164] where R1to R9are hydrogen or alkyl groups having from 1 to 6 carbon atoms, and m is a whole number from 0 to 20, g is a whole number from 0 to 10 and p is a whole number from 0 to 5. The radicals R' to R9are preferably hydrogen, where m is 0 or 1 and g is 1. The corresponding compounds are maleic acid, fumaric acid, maleic anhydride, allyl glycidyl ether and vinyl glycidyl ether.

[0165] Preferred compounds of the formulae I, II and IV are maleic acid, maleic anhydride and (meth)acrylates comprising epoxy groups, such as glycidyl acrylate and glycidyl methacrylate, and the esters with tertiary alcohols, such as tert-butyl acrylate. Although the latter have no free carboxy groups, their behavior approximates to that of the free acids and they are therefore termed monomers with latent carboxy groups.

[0166] The copolymers are advantageously composed of from 50 to 98 wt % of ethylene, from 0.1 to 20 wt % of monomers comprising epoxy groups and / or methacrylic acid and / or monomers comprising anhydride groups, the remaining amount being (meth)acrylates.

[0167] Particular preference is given to copolymers composed of: from 50 to 98 wt. %, in particular from 55 to 95 wt. % of ethylene, from 0.1 to 40 wt. %, in particular from 0.3 to 20 wt. %of glycidyl acrylate and / or glycidyl methacrylate, (meth)acrylic acid and / or maleic anhydride, and from 1 to 45 wt. %, in particular from 5 to 40 wt. % of n-butyl acrylate and / or 2-ethylhexyl acrylate.

[0168] Other preferred (meth)acrylates are the methyl, ethyl, propyl, isobutyl and tert-butyl esters. Co-monomers which may be used alongside these include vinyl esters and vinyl ethers.

[0169] The ethylene copolymers described above may be prepared by processes known per se, preferably by random copolymerization at high pressure and elevated temperature. Appropriate processes are well-known.

[0170] Other preferred elastomers are emulsion polymers whose preparation is described, for example, by Blackley in the monograph “Emulsion Polymerization”. The emulsifiers and catalysts which can be used are known per se.

[0171] In principle it is possible to use homogeneously structured elastomers or else those with a shell structure. The shell-type structure is determined by the sequence of addition of the individual monomers. The morphology of the polymers is also affected by this sequence of addition.

[0172] Monomers which may be mentioned here, merely as examples, for the preparation of the rubber fraction of the elastomers are acrylates, such as, for example, n-butyl acrylate and 2- ethylhexyl acrylate, corresponding methacrylates, butadiene and isoprene, and also mixtures of these.

[0173] These monomers may be copolymerized with other monomers, such as, for example, styrene, acrylonitrile, vinyl ethers and with other acrylates or methacrylates, such as methyl methacrylate, methyl acrylate, ethyl acrylate or propyl acrylate.

[0174] The soft or rubber phase (with a glass transition temperature of below 0° C.) of the elastomers may be the core, the outer envelope or an intermediate shell (in the case of elastomers whose structure has more than two shells). Elastomers having more than one shell may also have more than one shell composed of a rubber phase.

[0175] If one or more hard components (with glass transition temperatures above 20 °C) are involved, besides the rubber phase, in the structure of the elastomer, these are generally preparedby polymerizing, as principal monomers, styrene, acrylonitrile, methacrylonitrile, a- methylstyrene, p-methylstyrene, or acrylates or methacrylates, such as methyl acrylate, ethyl acrylate or methyl methacrylate. Besides these, it is also possible to use relatively small proportions of other comonomers.

[0176] UV stabilizers that may be mentioned, the amounts of which used are generally up to about 2 wt. %, based on the molding composition, are various substituted resorcinols, salicylates, benzotriazoles, and benzophenones.

[0177] Materials that can be added as colorants are inorganic pigments, such as titanium dioxide, ultramarine blue, iron oxide, and carbon black, and also organic pigments, such as phthalocyanines, quinacridones, perylenes, and also dyes, such as anthraquinones.

[0178] Materials that can be used as nucleating agents are sodium phenylphosphinate, aluminum oxide, silicon dioxide, and also preferably talc.

[0179] The thermoplastic molding compositions can furthermore contain flame retardants as component F.

[0180] As component F, the thermoplastic molding compositions of the present disclosure can include 1.0 to 10.0 wt. %, preferably 2.0 to 6.0 wt. %, in particular 3.0 to 5.0 wt. %, of at least one phosphazene of general formula (IX) or (X) as flame retardant.

[0181] Component F includes, in ssoommee embodiments, a mixture of cyclic phenoxyphosphazenes having three and four phenoxy phosphazene units. The weight ratio of rings including three phenoxyphosphazene units to rings including four phenoxyphosphazene units is preferably about 80:20. Larger rings of the phenoxyphosphazene units may likewise be present but in smaller amounts. Suitable cyclic phenoxyphosphazenes are obtainable from Fushimi Pharmaceutical Co., Ltd., under the name Rabitle® FP-100. This is a matte-white / yellowish solid having 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 wt. %.

[0182] The thermoplastic molding materials preferably comprise 1.0 to 6.0 wt. %, preferably 2.5 to 5.5 wt. %, in particular 3.0 to 5.0 wt. % of at least one aliphatic or aromatic ester of phosphoric acid or polyphosphoric acid as flame retardant.

[0183] For this reason, solid, non-migrating phosphate esters having a melting point between 70 °C and 150 °C are preferred. Without wishing to be bound by theory, the products from such phosphate esters are easy to meter and exhibit markedly less migration in the molding material. Particularly preferred examples are the commercially available phosphate esters PX-200 (CAS: 139189-30-3) from Daihachi, or Sol-DP from 1CL-IP. Further phosphate esters with appropriate substitution of the phenyl groups are conceivable when this allows the preferred melting range to be achieved. The general structural formula, depending on the substitution pattern in the ortho position or the para position on the aromatic ring, is as follows:

[0184] wherein:

[0185] R1= H, methyl, ethyl or isopropyl, but preferably H.

[0186] n = between 0 and 7, but preferably 0.

[0187] R2-6= H, methyl, ethyl or isopropyl, but preferably methyl. R6is preferably identical to R4and R5.

[0188] m = may be, but needs not be identical and is between 1, 2, 3, 4 and 5, but preferably2.

[0189] R" = may be H, methyl, ethyl or cyclopropyl, but preferably methyl and H.

[0190] It is particularly preferable when at least one aromatic ester of polyphosphoric acid is employed. Such aromatic polyphosphates are obtainable for example from Daihachi Chemical under the name PX-200.

[0191] As component F, the thermoplastic molding materials according to the invention can include 5.0 to 30.0 wt. %, preferably 10.0 to 25.0 wt. %, in particular 12.0 to 20.0 wt. %, for example about 16.0 wt. %, of at least one metal phosphinate or phosphinic acid salt described hereinbelow as flame retardant. Examples of preferred flame retardants of component F are metal phosphinates derived from hypophosphorous acid. A metal salt of hypophosphorous acid with Mg, Ca, Al or Zn as the metal may be employed for example. Particular preference is given here to aluminum hypophosphite.

[0192] Also suitable are phosphinic acid salts of formula (I) or / and diphosphinic acid salts of formula (II) or polymers thereof:

[0193] wherein R1and R2are identical or different and represent hydrogen, C1-C6-alkyl, linear or branched, and / or aryl;

[0194] R3represents Ci-Cio-alkylene, linear or branched, or C6-C10-arylene, -alkylarylene or -arylalkylene;

[0195] M represents Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K and / or a protonated nitrogen base;

[0196] m = 1 to 4; n = 1 to 4; x = 1 to 4, preferably m=3, x=3.

[0197] Preferably, R1, R2are identical or different and represent hydrogen, methyl, ethyl, n- propyl, isopropyl, n-butyl, tert-butyl, n-pentyl and / or phenyl.

[0198] Preferably, R3represents methylene, ethylene, n-propylene, isopropylene, n-butylene, tert-butylene, n-pentylene, n-octylene oorr n-dodecylene, phenylene oorr naphthylene; methylphenylene, ethylphenylene, tert-butylphenylene, methylnaphthylene, ethylnaphthylene or tert-butylnaphthylene; phenylmethylene, phenylethylene, phenylpropylene or phenylbutylene.

[0199] Particularly preferably, R1, R2are hydrogen, methyl, or ethyl, and M is Al; particular preference is given to Al hypophosphite.

[0200] Further flame retardants are, for example, halogen-containing flame retardants. Suitable halogen-containing flame retardants are preferably brominated compounds, such as brominated diphenyl ether, brominated trimethylphenylindane (FR 1808 from DSB) tetrabromobisphenol A and hexabromocyclododecane. Suitable flame retardants are preferably brominated compounds, such as brominated oligocarbonates (BC 52 or BC 58 from Great Lakes)

[0201] The brominated oligostyrenes preferably employed as flame retardants have an average degree of polymerization (number-average) between 3 and 90, preferably between 5 and 60, measured by vapor pressure osmometry in toluene. Cyclic oligomers are likewise suitable.

[0202] In some embodiments, no halogen-containing flame retardants are employed in the thermoplastic molding compositions. A flame retardant melamine compound suitable as component F is, for example, a melamine compound which, when added to glass fiber filled polyamide molding materials, reduces flammability and influences fire behavior in a fire retarding fashion, thus resulting in improved properties in the UL 94 tests and in the glow wire test.

[0203] The melamine compound can be, for example, selected from melamine borate, melamine phosphate, melamine sulfate, melamine pyrophosphate, melam, melem, melon or melamine cyanurate or mixtures thereof. The melamine cyanurate preferentially suitable according to the invention is a reaction product of preferably equimolar amounts of melamine and cyanuric acid / isocyanuric acid.

[0204] Further suitable compounds (often also described as salts or adducts) are melamine sulfate, melamine, melamine borate, oxalate, phosphate prim., phosphate sec. and pyrophosphate sec., melamine neopentyl glycol borate. In some embodiments, the molding materials are preferably free from polymeric melamine phosphate (CAS no. 56386-64-2 or 218768-84-4).

[0205] This is to be understood as meaning melamine polyphosphate salts of a 1,3, 5 -triazine compound which have an average degree of condensation number n between 20 and 200 and a 1,3,5-triazine content of 1.1 to 2.0 mol of a 1,3, 5 -triazine compound selected from the group consisting of melamine, melam, melem, melon, ammeline, ammelide, 2-ureidomelamine, acetoguanamine, benzoguanamine and diaminophenyltriazine per mole of phosphorus atom. Preferably, the n-value of such salts is generally between 40 and 150 and the ratio of a 1,3,5- triazine compound per mole of phosphorus atom is preferably between 1.2 and 1.8. Furthermore,the pH of a 10 wt. % aqueous slurry of salts produced according to EP-B1 095030 will generally be more than 4.5 and preferably at least 5.0. The pH is typically determined by adding 25 g of the salt and 225 g of clean water at 25 °C into a 300 mL beaker, stirring the resultant aqueous slurry for 30 minutes and then measuring the pH. The abovementioned n-value, the number-average degree of condensation, may be determined by means of31P solid-state NMR. J. R. van Wazer, C. F. Callis, J. Shoolery and R. Jones, J. Am. Chem. Soc., 78, 5715, 1956 discloses that the number of adjacent phosphate groups gives a unique chemical shift which permits clear distinction between orthophosphates, pyrophosphates, and polyphosphates.

[0206] Also employable as component F are functional polymers, which may be flameretardant polymers. Such polymers are described in U.S. Patent No. 8,314,202 and include 1,2- bis[4-(2-hydroxyethoxy)phenyl]ethanone repeating units. A further suitable functional polymer for increasing the amount of carbon residue includes poly(2,6-dimethyl-l,4-phenyleneoxide) (PPPO).

[0207] The thermoplastic molding compositions of the invention can be produced by processes known per se, by mixing the starting components in conventional mixing apparatus, such as screw-based extruders, Brabender mixers, or Banbury mixers, and then extruding the same. After extrusion, the extrudate can be cooled and pelletized. It is also possible to premix individual components and then to add the remaining starting materials individually and / or likewise in the form of a mixture. The mixing temperatures are generally from about 230 °C to about 320 °C.

[0208] These materials are suitable for the production of fibers, foils, and moldings of any type. Some examples follow: cylinder head covers, motorcycle covers, intake manifolds, chargeair-cooler caps, plug connectors, gearwheels, cooling-fan wheels, and cooling-water tanks.

[0209] In the electrical and electronic sector, improved-flow polyamides can be used to produce plugs, plug parts, plug connectors, membrane switches, printed circuit board modules, microelectronic components, coils, I / O plug connectors, plugs for printed circuit boards (PCBs), plugs for flexible printed circuits (FPCs), plugs for flexible integrated circuits (FFCs), high-speed plug connections, terminal strips, connector plugs, device connectors, cable-harness components, circuit mounts, circuit-mount components, three-dimensionally injection-molded circuit mounts, electrical connection elements, and mechatronic components.

[0210] Possible uses in automobile interiors are for dashboards, steering-column switches, seat components, headrests, center consoles, gearbox components, and door modules, and possible uses in automobile exteriors are for door handles, exterior-mirror components, windshield-wiper components, windshield-wiper protective housings, grilles, roof rails, sunroof frames, engine covers, cylinder-head covers, intake pipes (in particular intake manifolds), windshield wipers, and also external bodywork components.

[0211] Without wishing to be bound by theory, it is contemplated that the combination of components B, C, and D lead to an efficient system to stabilize polyamides at 180 °C and above, while maintaining a completely metal halide-free system. That is, the combination of components B, C, D provides an unexpected stabilizing effect to heat-aging. Either of B, C, or D alone is not sufficient to produce the stabilizing effect, and the components B, C, and D work in a synergistic manner.

[0212] In some embodiments, the thermoplastic molding compositions are totally halide-free, so that they also do not contain halogen-containing flame retardants.

[0213] The molded articles from the above compositions exhibit better heat-aging resistant than currently available halide or non-halide based stabilizer systems disclosed. Thermoplastic parts that are exposed to prolong period of exposures to heat, such as automotive components like a cylinder head cover, can achieve longer lifetimes if made with the disclosed compositions. Additionally, improved HAR can also permit the use of the components at higher temperatures.

[0214] 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, and so forth.

[0215] In some embodiments, the thermoplastic molding composition has a tensile strength of at least about 200 MPa at 23 °C after aging for 3000 hours at 180 °C, such as at least about 200 MPa, at least about 210 MPa, at least about 215 MPa, at least about 220 MPa, and so forth.

[0216] In some embodiments, the thermoplastic molding composition has a tensile strength retention of at least about 50% after aging for 3000 hours at 180 °C, 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%, atleast about 97%, at least about 98%, at least about 99%, about 100%, or any value contained within a range formed by any two of the preceding values.

[0217] In some embodiments, the thermoplastic molding composition has a tensile strength of at least about 150 MPa at 23 °C after aging for 5000 hours at 180 °C, 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, and so forth.[0218[ In some embodiments, the thermoplastic molding composition has a tensile strength retention of at least about 40% after aging for 5000 hours at 180 °C, 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%, and so forth.

[0219] FIG. 1 is graph of retention of tensile strength of the compositions of the present disclosure after heat aging at 180 °C over a time of 5000 hours. As shown in FIG. 1, the compositions of the present disclosure offer a tensile strength retention of at least about 70% after heat aging.

[0220] In some embodiments, the thermoplastic molding composition has a tensile elongation at break of about 2.0% to about 4.0% at 23 °C. For example, in some embodiments, the thermoplastic molding composition can have a tensile elongation at break of 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%, about3.6%, about 3.7%, about 3.8%, about 3.9%, about 4.0%, or any value contained within a range formed by any two of the preceding values.

[0221] In some embodiments, the thermoplastic molding composition has a tensile elongation at break of about 1.2% to about 2.5% at 23 °C after heat aging for 5000 hours at 180 °C, 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 contained within a range formed by any two of the preceding values.

[0222] In some embodiments, the thermoplastic molding composition has a tensile elongation at break retention of at least about 50% after aging for 3000 hours at 180 °C, such as at least about 50%, at least about 55%, at least about 60%, at least about 65%, at least about 70%, and so forth.

[0223] In some embodiments, the thermoplastic molding composition has a tensile elongation at break retention of at least about 40% after aging for 5000 hours at 180 °C, such as at least about 40%, at least about 45%, at least about 50%, and so forth.

[0224] FIG. 2 is graph of retention of tensile elongation of the compositions of the present disclosure after heat aging at 180 °C over a time of 5000 hours. As shown in FIG. 2, the compositions of the present disclosure exhibit a tensile elongation retention of at least about 50% after heat aging as described herein for 3000 hours and at least about 40% after heat aging as described herein for 5000 hours.

[0225] In some embodiments, the thermoplastic molding composition has a notched Izod impact retention of at least about 95% after aging for 3000 hours at 180 °C, such as about 95%, about 96%, about 97%, about 98%, about 99%, about 100%, or any value contained within a range formed by any two of the preceding values. In some embodiments, the thermoplastic molding composition has a notched Izod impact retention of at least about 90% after aging for 5000 hours at 180 °C, 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 contained within a range formed by any two of the preceding values.

[0226] FIG. 3 is graph of retention of notched Izod impact (Nil) of the compositions of the present disclosure after heat aging at 180 °C over a time of 5000 hours. As shown in FIG. 3, the compositions of the present disclosure exhibit an Nil retention of at least about 95% after heat aging as described herein for 3000 hours and at least about 90% after heat aging as described herein for 5000 hours.EXAMPLES

[0227] The following thermoplastic molding compositions were prepared as shown in TABLE 1.

[0229] TABLE 2 shows the tensile properties of the dry-as-molded tensile properties tested at 23 °C as well as the percent retention of tensile properties after the parts experienced 3000 hrs of heat aging at 180 °C. Composition 3 retains 16%-35% additional tensile strength compared tothe copper halide based systems (Composition 1 and Composition 4, respectively) and 8% additional tensile strength compared to Composition 2.

[0231] TABLE 3 shows the tensile elongation properties of the compositions after 3000 hrs of heat aging at 180 °C. Composition 3 retains 25%-30% additional tensile elongation compared to the copper halide based systems (Composition 1 and Composition 4, respectively) and 18% additional tensile elongation compared to Composition 2.

[0232] TABLE 3

[0233] TABLE 4 shows the tensile properties of the dry-as-molded tensile properties tested at 23 °C as well as the percent retention of tensile properties after the parts experienced 5000 hrs of heat aging at 180 °C. Composition 3 retains 20%-49% additional tensile strength compared to the copper halide based systems (Composition 1 and Composition 4, respectively) and 20% additional tensile strength compared to Composition 2.

[0234] TABLE 4

[0235] TABLE 5 shows the tensile elongation properties of the compositions after 5000 hrs of heat aging at 180 °C. Composition 3 retains 19%-29% additional tensile elongation compared to the copper halide-based systems (Composition 1 and Composition 4, respectively) and 16% additional tensile elongation compared to Composition 2.

[0237] TABLE 6 shows the notched Izod impact strength of the compositions 3000 hrs of heat aging at 180 °C. Composition 3 retains 27%-20% additional impact strength compared to the copper halide-based systems (Composition 1 and Composition 4, respectively) and 22% additional impact strength compared to Composition 2.

[0238] TABLE 6

[0239] TABLE 7 shows the notched Izod impact strength of the compositions 5000 hrs of heat aging at 180 °C. Composition 3 retains 38%-67% additional impact strength compared to the copper halide-based systems (Composition 1 and Composition 4, respectively) and 11% additional impact strength compared to Composition 2.

[0240] TABLE 7

[0241] This disclosure is not limited to the particular systems, devices and methods described, as these may vary. The terminology used in the description is for the purpose of describing the particular versions or embodiments only and is not intended to limit the scope.

[0242] As used in this document, the singular forms “a,” “an,” and “the” include plural references unless the context clearly dictates otherwise. Unless defined otherwise, all technical and scientific terms used herein have the same meanings as commonly understood by one of ordinary skill in the art. Nothing in this disclosure is to be construed as an admission that the embodiments described in this disclosure are not entitled to antedate such disclosure by virtue of prior invention. As used in this document, the term “comprising” means “including, but not limited to.”

[0243] As used herein, the term “about” means plus or minus 10% of the numerical value of the number with which it is being used. For example, “about 50%” means in the range of 45-55%.

[0244] In the above detailed description, reference is made to the accompanying drawings, which form a part hereof. In the drawings, similar symbols typically identify similar components, unless context dictates otherwise. The illustrative embodiments described in the detailed description, drawings, and claims are not meant to be limiting. Other embodiments may be used,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 the aspects of the present disclosure, as generally described herein, and illustrated in the Figures, can be arranged, substituted, combined, separated, and designed in a wide variety of different configurations, all of which are explicitly contemplated herein.

[0245] The present disclosure is not to be limited in terms of the particular embodiments described in this application, which are intended as illustrations of various aspects. Many modifications and variations can be made without departing from its spirit and scope, as will be apparent to those skilled in the art. Functionally equivalent methods and apparatuses within the scope of the disclosure, in addition to those enumerated herein, will be apparent to those skilled in the art from the foregoing descriptions. Such modifications and variations are intended to fall within the scope of the appended claims. The present disclosure is to be limited only by the terms of the appended claims, along with the full scope of equivalents to which such claims are entitled. It is to be understood that this disclosure is not limited to particular methods, reagents, compounds, compositions or biological systems, which can, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.

[0246] With respect to the use of substantially any plural and / or singular terms herein, those having skill in the art can translate from the plural to the singular and / or from the singular to the plural as is appropriate to the context and / or application. The various singular / plural permutations may be expressly set forth herein for sake of clarity.

[0247] It will be understood by those within the art that, in general, terms used herein, and especially in the appended claims (for example, bodies of the appended claims) are generally intended as “open” terms (for example, the term “including” should be interpreted as “including but not limited to,” the term “having” should be interpreted as “having at least,” the term “includes” should be interpreted as “includes but is not limited to,” et cetera). While various compositions, methods, and devices are described in terms of “comprising” various components or steps (interpreted as meaning “including, but not limited to”), the compositions, methods, and devices can also “consist essentially of’ or “consist of” the various components and steps, and such terminology should be interpreted as defining essentially closed-member groups. It will be furtherunderstood by those within the art that if a specific number of an introduced claim recitation is intended, such an intent will be explicitly recited in the claim, and in the absence of such recitation no such intent is present.

[0248] For example, as an aid to understanding, the following appended claims may contain usage of the introductory phrases "at least one" and "one or more" to introduce claim recitations. However, the use of such phrases should not be construed to imply that the introduction of a claim recitation by the indefinite articles "a" or "an" limits any particular claim containing such introduced claim recitation to embodiments containing only one such recitation, even when the same claim includes the introductory phrases "one or more" or "at least one" and indefinite articles such as "a" or "an" (for example, “a” and / or “an” should be interpreted to mean “at least one” or “one or more”); the same holds true for the use of definite articles used to introduce claim recitations.

[0249] In addition, even if a specific number of an introduced claim recitation is explicitly recited, those skilled in the art will recognize that such recitation should be interpreted to mean at least the recited number (for example, the bare recitation of "two recitations," without other modifiers, means at least two recitations, or two or more recitations). Furthermore, in those instances where a convention analogous to “at least one of A, B, and C, et cetera” is used, in general such a construction is intended in the sense one having skill in the art would understand the convention (for example, “a system having at least one of A, B, and C” would include but not be limited to systems that have A alone, B alone, C alone, A and B together, A and C together, B and C together, and / or A, B, and C together, et cetera). In those instances where a convention analogous to “at least one of A, B, or C, et cetera” is used, in general such a construction is intended in the sense one having skill in the art would understand the convention (for example, “a system having at least one of A, B, or C” would include but not be limited to systems that have A alone, B alone, C alone, A and B together, A and C together, B and C together, and / or A, B, and C together, et cetera). It will be further understood by those within the art that virtually any disjunctive word and / or phrase presenting two or more alternative terms, whether in the description, claims, or drawings, should be understood to contemplate the possibilities of including one of the terms, either of the terms, or both terms. For example, the phrase “A or B” will be understood to include the possibilities of “A” or “B” or “A and B.”

[0250] In addition, where features or aspects of the disclosure are described in terms of Markush groups, those skilled in the art will recognize that the disclosure is also thereby described in terms of any individual member or subgroup of members of the Markush group.

[0251] As will be understood by one skilled in the art, for any and all purposes, such as in terms of providing a written description, all ranges disclosed herein also encompass any and all possible subranges and combinations of subranges thereof. Any listed range can be easily recognized as sufficiently describing and enabling the same range being broken down into at least equal halves, thirds, quarters, fifths, tenths, et cetera. As a non-limiting example, each range discussed herein can be readily broken down into a lower third, middle third and upper third, et cetera. As will also be understood by one skilled in the art all language such as “up to,” “at least,” and the like include the number recited and refer to ranges that can be subsequently broken down into subranges as discussed above. Finally, as will be understood by one skilled in the art, a range includes each individual member. Thus, for example, a group having 1-3 compounds refers to groups having 1, 2, or 3 compounds. Similarly, a group having 1-5 cells refers to groups having 1, 2, 3, 4, or 5 compounds, and so forth.

[0252] Various of the above-disclosed and other features and functions, or alternatives thereof, may be combined into many other different systems or applications. Various presently unforeseen or unanticipated alternatives, modifications, variations, or improvements therein may be subsequently made by those skilled in the art, each of which is also intended to be encompassed by the disclosed embodiments.

Claims

What is claimed is:

1. A thermoplastic molding composition, comprising: about 30 wt. % to about 99.9 wt. % of at least one thermoplastic polyamide as component A; about 0.1 wt. % to about 10 wt. % of at least one polyhydric alcohol having more than six hydroxyl groups and having a number average molecular weight Mnof greater than 2000 g / mol as component B; about 0.05 wt. % to about 3 wt. % of at least one sterically hindered phenol antioxidant as component C; about 0.1 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 and / or particulate filler as component E;0 to about 25 wt. % of further additives as component F; wherein the total wt. % of components A through F is 100 wt. %.

2. The thermoplastic molding composition of claim 1, comprising about 45 wt. % to about 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 (PA 12), polyamide 610 (PA610), polyamide 46 (PA46), or combinations thereof.

4. The thermoplastic molding composition of claim 1, comprising about 1 wt. % to about 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], pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionate], distearyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 2,6,7- trioxa-l-phosphabicyclo[2.2.2]oct-4-ylmethyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate,3.5-ditert-butyl-4-hydroxyphenyl-3,5-distearylthiotriazylamine, 2-(2'-hydroxy-3 '-hydroxy- 3', 5'-di-tertbutylphenyl)-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-hydroxyhydrocinnamide, or combinations thereof.

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

9. The thermoplastic molding composition of claim 1, wherein component D has a number average molecular weight Mnof greater than about 1000 g / mol.

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

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 about 10 wt. % to about 50 wt. % 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, lamellarnanofillers, acicular nanofillers, boehmite, bentonite, montmorillonite, vermiculite, hectorite, 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 for 3000 hours at 180 °C.

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 for 3000 hours at 180 °C.

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 for 5000 hours at 180 °C.

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 for 5000 hours at 180 °C.

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 for 3000 hours at 180 °C.

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 for 3000 hours at 180 °C.

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 for 5000 hours at 180 °C.

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 for 3000 hours at 180 °C.

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 for 5000 hours at 180 °C.

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