Thermoplastic molding composition, process for preparing thermoplastic molding composition, use of thermoplastic molding composition, fiber, sheet or mold, and use of a compound.

Abstract

THERMOPLASTIC MOLDING COMPOSITION, PROCESS FOR PREPARING THE THERMOPLASTIC MOLDING COMPOSITION, USE OF THE THERMOPLASTIC MOLDING COMPOSITION, FIBER, SHEET OR MOLD AND USE OF A COMPOUND. The invention relates to a thermoplastic molding composition comprising a) 39.9 to 99.9% by weight of at least one thermoplastic polyamide as component A; b) 0.1 to 10% by weight of at least one plasticizer of the general formula (1); R1-O-(CH2CH2-O-)nR2 (1); with n = 1 to 10; R1, R2 being independently H, C1-12 alkyl, phenyl or tolyl, with a boiling point above 250 °C, as component B; c) 0 to 45% by weight of at least one elastomeric polymer as component C; d) 0 to 60% by weight of at least one fibrous and / or particulate filler as component D; e) 0 to 25% by weight of additional additives as component E; where the total % by weight of components A to E is 100% by weight.

Description

Thermoplastic molding composition, process for preparing thermoplastic molding composition, use of thermoplastic molding composition, fiber, SHEET OR MOLD AND USE OF A COMPOUND Field of Invention

[001] The invention relates to thermoplastic molding compositions comprising polyamide and a plasticizer.

[002] The invention also relates to the use of the molding compositions of the invention for the production of fibers, sheets and molds of any kind, and also to the resulting fibers, sheets and molds.

[003] Furthermore, the invention relates to the use of a specific compound as a plasticizer for polyamides.

[004] Polyamides can be modified by adding plasticizers to obtain a reduced modulus of elasticity (tensile modulus) and greater flexibility. The plasticizer typically lowers the glass transition temperature of the polyamide. The use of plasticizers in polyamides results in specific mechanical properties. Plasticized polyamide typically has a lower E-modulus and a higher elongation at break when compared to a polyamide without plasticizer. In addition, plasticized polyamides typically have increased impact resistance compared to non-plasticized polyamides. Background of the Invention

[005] Typical applications for modified polyamides include extruded tubing, for example, for the automotive sector, such as brake fluid tubing. Other applications include cable conduit systems or cable management systems, shoe soles, dies for the preparation of rubber hoses (mandrels), and sporting goods such as ski boots or football shoes. Petition 870240105284, dated 10 / 12 / 2024, page 14 / 95 2 / 77

[006] Suitable plasticizers are typically low molecular weight compounds.

[007] Kunststoff-Handbuch, Band VI Polyamide, Carl Hanser Verlag München 1966, Sections 3.4.2.1. b) on pages 238 and 239 in connection with Table 7 describes suitable plasticizers. They can be divided into hydroxy aromatic compounds, sulfonamides and other plasticizers such as lactams, lactones, alcohols etc.

[008] Document WO 2015 / 127048 A1 discloses poly(trimethylene ether) glycol (PPD) as a plasticizer for polyamides. Examples refer to poly(trimethylene ether) glycol (PPD) with a number average molecular weight of 255 and poly(trimethylene ether) glycol benzoate (PPDB). Among the commercial plasticizers mentioned are N-butylbenzene sulfonamide (NBBS) and polyethylene glycol dibenzoate (Mn = 410) and poly(1,2-propylene glycol) dibenzoate (Mn = 400).

[009] US Patent 2,214,405 discloses monomeric amides, specifically sulfonamides, for example, N-alkylarylsulfonamides, as plasticizers for polyamides.

[010] Publication EP 1 873 200 A1 discloses different plasticizers for aliphatic polyamides, including p-alkylbenzenesulfonamides and guanidine-based compounds.

[011] Document WO 2010 / 137725 A1 refers to a polyamide resin composition obtained by incorporating into a polyamide resin: an inorganic filler that has been surface-treated with an organopolysiloxane and in which the ratio between the amount of organopolysiloxane used for the treatment and the specific surface area is in a specific range (A); and a polyalkylene glycol (B) with a number average molecular weight of 200 or more and 4,000 or less and / or a partial ester compound of a fatty acid with an alkylene oxide adduct of an alcohol Petition 870240105284, dated 10 / 12 / 2024, p. 15 / 95 3 / 77 polyhydric (C).

[012] Document CN 107760022 A refers to a hardened plasticized nylon 6 material comprising, by mass, 73.6 - 84.5% nylon 6, 10 - 15% of a hardening agent, 10 - 15% of a plasticizer, 0.2 - 0.6% of a heat stabilizer and 0.3 - 0.8% of a lubricant. The hardening agent is a maleic anhydride grafted polyolefin hardening agent, the plasticizer is a mixture of lactam compounds and polyethylene glycol, the heat stabilizer is a mixture of a phenolic antioxidant and a thioester antioxidant and the lubricant is montan wax. Based on traditional tempered nylon 6, a third-component plasticizer is used so that the hardened, plasticized nylon 6 material significantly reduces the percentage of hardening agent, retains the high toughness of the nylon 6 material, greatly improves the flowability of the nylon 6 material, and has an expanded application range for the nylon 6 material.

[013] US patent 2015 / 051329 A1 refers to a polymer composition comprising an effective amount of plasticizer in a polyamide base polymer, wherein the plasticizer comprises an aromatic ester of poly(trimethylene ether) glycol with a number average molecular weight of 1000 or less.

[014] Most of the compounds mentioned above are toxic, for example, benzenesulfonamide. Lactams, such as caprolactam, lead to significant emissions during the processing of the molding composition and the final molded parts.

[015] The underlying objective of the present invention is to provide a plasticizer for polyamides that has high plasticizing efficiency, low migration in the polyamide, and is not problematic with respect to the Globally Harmonised System of Classification and Labelling of Chemicals. Petition 870240105284, dated 10 / 12 / 2024, page 16 / 95 4 / 77 (GHS, acronym for Globally Harmonized System of classification and labeling of chemicals). Description of the Invention

[016] The objective is achieved according to the present invention by a thermoplastic molding composition comprising: (a) 39.9 to 99.9% by weight of at least one thermoplastic polyamide as component A, (b) 0.1 to 10% by weight of at least one plasticizer of general formula (1): R1-O-(CH2CH2-O-)nR2 (1) with n = 1 to 10 Ri, R2 being independently H, C1-12 alkyl, phenyl or tolyl, with a boiling point above 250 °C, as component B, (c) 0 to 45% by weight of at least one elastomeric polymer as component C, (d) 0 to 60% by weight of at least one fibrous and / or particulate filler as component D, (e) 0 to 25% by weight of additional additives as component E, wherein the total % by weight of components A to E is 100% by weight.

[017] Furthermore, the objective is achieved by using a compound of the general formula (1): R1-O-(CH2CH2-O-)nR2 (1) with n = 1 to 10 R1, R2 being, independently, H, C1-12 alkyl, phenyl or tolyl, with a boiling point above 250 °C as a plasticizer for thermoplastic polyamides. Petition 870240105284, dated 10 / 12 / 2024, page 17 / 95 5 / 77

[018] Furthermore, the objective is achieved by the above thermoplastic molding composition preparation process, mixing components A to E.

[019] Furthermore, the objective is achieved by using the thermoplastic molding composition for the production of fibers, sheets and molds, and by the fibers, sheets and molds produced from the thermoplastic molding composition.

[020] According to the present invention, (poly)ethylene glycols have been found to be very efficient plasticizers for polyamides. They are significantly more efficient in decreasing the modulus of elasticity of polyamide molding compositions than known compounds, specifically sulfonamides such as N-(2-hydroxypropyl)benzenesulfonamide or caprolactam or lauryl-lactam. Furthermore, they do not migrate from the molding composition and molds.

[021] Thus, the present invention is based on the combination of components A and B or on the use of component B as a plasticizer in polyamides.

[022] Preferably, the amount of lactam in thermoplastic molding compositions according to the present invention is less than 3% by weight, more preferably less than 2% by weight, based on the total amount of the thermoplastic molding composition (which is 100% by weight).

[023] The number average molecular weight, as well as the weight average molecular weight (Mn and Mw, respectively) and polydispersity data of the compounds used in the molding composition can be obtained using gel permeation chromatography (GPC) in hexafluoroisopropanol as solvent with PMMA calibration.

[024] The ISO standards refer to the 2020 version.

[025] This molecular weight determination can be used Petition 870240105284, dated 10 / 12 / 2024, p. 18 / 95 6 / 77 for all components of thermoplastic molding compositions according to the present invention.

[026] The molding compositions of the invention comprise, as component A, from 39.9 to 99.9% by weight, preferably from 45 to 99.5% by weight, and in particular from 49 to 99.9% by weight of at least one thermoplastic polyamide.

[027] If components C, D, or E, or combinations thereof, are present in the thermoplastic molding composition, the maximum quantity of component A decreases by the minimum quantity of each of components C, D, or E, or a combination thereof.

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

[029] Preference is given to semicrystalline or amorphous resins with a molecular weight (weight average) of at least 5,000, described by way of example in the following US patents: US 2,071,250, US 2,071,251, US 2,130,523, US 2,130,948, US 2,241,322, US 2,312,966, US 2,512,606 and US 3,393,210.

[030] Examples of these are polyamides derived from lactams that have from 7 to 13 members in the ring, for example, polycaprolactam, polycaprylolactam and polylaurolactam, and also polyamides obtained by the reaction of dicarboxylic acids with diamines.

[031] The dicarboxylic acids that can be used are alkanedicarboxylic acids with 6 to 12, in particular 6 to 10 carbon atoms, and aromatic dicarboxylic acids. Simply as examples, those that can be mentioned here are adipic acid, azelaic acid, sebacic acid, Petition 870240105284, dated 10 / 12 / 2024, p. 19 / 95 7 / 77 dodecanedioic acid and terephthalic and / or isophthalic acid

[032] Particularly suitable diamines are alkanediamines with 6 to 12, in particular 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 1,5-diamino-2-methylpentane.

[033] Preferred polyamides are polyhexamethylene adipamide, polyhexamethylene sebacamide and polycaprolactam and also nylon-6 / 6,6 copolyamides, in particular having a proportion of 5 to 95% by weight of caprolactam units (e.g., Ultramid® C31 from BASF SE).

[034] Other suitable polyamides can be obtained starting from ω-aminoalkylnitriles, for example, aminocapronitrile (PA 6) and adiponitrile with hexamethylenediamine (PA 66) by means of the reaction known as direct polymerization in the presence of water, for example, as described in documents DE-A 10313681, EP-A 1198491 and EP 922065.

[035] Mention may also be made of polyamides that can be obtained, for example, by condensation of 1,4-diaminobutane with adipic acid at an elevated temperature (nylon-4,6). The processes for the preparation of polyamides of this structure are described, for example, in documents EP-A 38 094, EP-A 38 582 and EP-A 39 524.

[036] Other suitable examples are polyamides that can be obtained by copolymerization of two or more of the monomers mentioned above 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 mixtures of nylon-6 and nylon-66, and nylon-6 / 6,6 copolyamides and nylon-6,6 / 6 copolyamides.

[037] Other copolyamides that have been shown to be particularly advantageous are semi-aromatic copolyamides, such as PA 6 / 6T. Petition 870240105284, dated 10 / 12 / 2024, p. 20 / 95 8 / 77 and PA 66 / 6T, wherein the triamine content thereof is less than 0.5% by weight, preferably less than 0.3% by weight (see EP-A 299 444). Other high-temperature resistant polyamides are known from document EP-A 1994075 (PA 6T / 6I / MXD6).

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

[039] The following list, which is not exhaustive, comprises the polyamides A) mentioned and other polyamides A) for the purposes of the invention and the monomers contained therein:

[040] AB Polymers: PA 4 Pirrolidone PA 6 ε-Caprolactam PA 7 Ethanolactam PA 8 Caprylolactam PA 9 9-aminopelargonic acid PA 11 11-aminoundecanoic acid PA 12 Laurolactam

[041] AA / BB Polymers: PA 46 Tetramethylenediamine, adipic acid PA 66 Hexamethylenediamine, adipic acid PA 69 Hexamethylenediamine, azelaic acid PA 610 Hexamethylenediamine, sebacic acid PA 612 Hexamethylenediamine, decanedicarboxylic acid PA 613 Hexamethylenediamine, undecanedicarboxylic acid PA 1212 1,12-Dodecanediamine, decanedicarboxylic acid PA 1313 1,13-Diaminotridecane, undecanedicarboxylic acid PA 6T Hexamethylenediamine, terephthalic acid Petition 870240105284, dated 10 / 12 / 2024, page 21 / 95 9 / 77 PA MXD6 m-Xylylenediamine, adipic acid

[042] AA / BB Polymers: PA 6I Hexamethylenediamine, isophthalic acid PA 6-3-T Trimethylhexamethylenediamine, terephthalic acid PA 6 / 6.36 (see below) PA 6 / 6T (see PA 6 and PA6T) PA 6 / 66 (see PA 6 and PA66) PA 6 / 12 (see PA 6 and PA12) PA 66 / 6 / 610 (see PA 66, PA 6 and PA 610) PA 6I / 6T (see PA 6I and PA 6T) PA PACM 12 Diaminodicyclohexylmethane, laurolactam PA 6I / 6T / PACM as PA 6I / 6T + diaminodicyclohexylmethane PA 12 / MACMI Laurolactam, dimethyldiaminodicyclohexylmethane, isophthalic acid PA 12 / MACMT Laurolactam, dimethyldiaminodicyclohexylmethane, terephthalic acid PA PDA-T Phenylenediamine, terephthalic acid

[043] PA 6, PA 66, PA 6 / 66, PA 66 / 6, PA 12, PA 6.10, PA 6T / 6, PA 6I / 6T, PA 6T / 6I, PA 9T, PA 4T and copolyamides produced by polymerization of the components are preferred: (A') 15% to 84% by weight of at least one lactam, (B') 16% to 85% by weight of a mixture of monomers (M) comprising the components, (B1') at least one C32-C40 dimeric acid, and (B2') at least one C4-C12 diamine, wherein the percentages by weight of components (A') and (B') are Petition 870240105284, dated 10 / 12 / 2024, page 22 / 95 10 / 77 in each case based on the sum of the weight percentages of components (A') and (B'), specifically PA 6 / 6.36.

[044] The most preferred are PA 6, PA 66, PA 6 / 66 and PA 66 / 6, as well as PA 6 / 6.36.

[045] Suitable copolyamides are constructed from: (A1) 20.0 to 90.0% by weight of units derived from terephthalic acid and hexamethylenediamine, (A2) 0 to 50.0% by weight of units derived from εcaprolactam, (A3) 0 to 80.0% by weight of units derived from adipic acid and hexamethylenediamine, (A4) 0 to 40.0% by weight of other polyamide-forming monomers, wherein the proportion of component (A2) or (A3) or (A4), or mixtures thereof, is at least 10.0% by weight.

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

[047] In addition to units derived from terephthalic acid and hexamethylenediamine, copolyamides optionally comprise units derived from ε-caprolactam and / or units derived from adipic acid and hexamethylenediamine and / or units derived from other polyamide-forming monomers.

[048] Aromatic dicarboxylic acids (A4) comprise 8 to 16 carbon atoms. Suitable aromatic dicarboxylic acids include, for example, isophthalic acid, substituted terephthalic and isophthalic acids, such as 3-t-butylophthalic 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, Petition 870240105284, dated 10 / 12 / 2024, page 23 / 95 11 / 77 phenoxyterephthalic acid, with isophthalic acid being particularly preferred.

[049] Other monomers forming polyamide A4) may be derived from dicarboxylic acids with 4 to 16 carbon atoms and aliphatic or cycloaliphatic diamines with 4 to 16 carbon atoms, and also from corresponding aminocarboxylic acids / lactams with 7 to 12 carbon atoms. Examples of suitable monomers of these types mentioned 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, waminin indecanoic acid, and laurolactam as representatives of lactams / aminocarboxylic acids.

[050] Such suitable copolyamides are further elucidated in document DE-A-10 2009 011 668.

[051] As component A, thermoplastic molding materials may comprise at least one copolyamide produced by the polymerization of the components: (A') 15% to 84% by weight of at least one lactam, (B') 16% to 85% by weight of a mixture of monomers (M) comprising components (B1') at least one C32-C40 dimeric acid and (B2') at least one C4-C12 diamine, Wherein the weight percentages of components (A') and (B') are in each case based on the sum of the weight percentages of components (A') and (B').

[052] In the context of the present invention, the terms “component (A')” and “at least one lactam” are used synonymously and therefore have Petition 870240105284, dated 10 / 12 / 2024, page 24 / 95 12 / 77 same meaning.

[053] The same applies to the terms “component (B')” and “monomer mixture (M)”. These terms are also used synonymously in the context of the present invention and therefore have the same meaning.

[054] According to the invention, at least one copolyamide is produced by polymerizing 15% to 84% by weight of component (A') and 16% to 85% by weight of component (B'), preferably by polymerizing 40% to 83% by weight of component (A') and 17% to 60% by weight of component (B') and especially preferably by polymerizing 60% to 80% by weight of component (A') and 20% to 40% by weight of component (B'), wherein each of the weight percentages of components (A') and (B') is based on the sum of the weight percentages of components (A') and (B').

[055] The sum of the weight percentages of components (A') and (B') is preferably 100% by weight.

[056] It will be understood that the weight percentages of components (A') and (B') refer to the weight percentages of components (A') and (B') before polymerization, i.e., when components (A') and (B') have not yet reacted with each other. During the polymerization of components (A') and (B') the weight ratio of components (A') and (B') may optionally vary.

[057] According to the invention, at least one copolyamide is produced by the polymerization of components (A') and (B'). The polymerization of components (A') and (B') is known to those skilled in the art. The polymerization of components (A') with (B') is typically a condensation reaction. During the condensation reaction, component (A') reacts with components (B1') and (B2') present in component (B') and optionally with component (B3') described below, which may also be present in component (B'). This causes amide bonds to form between the individual components. During polymerization, component (A') is Petition 870240105284, dated 10 / 12 / 2024, p. 25 / 95 13 / 77 typically at least partially in open-chain form, that is, in the form of an amino acid.

[058] The polymerization of components (A') and (B') can occur in the presence of a catalyst. Suitable catalysts include all catalysts known to those skilled in the art that catalyze the polymerization of components (A') and (B'). Such catalysts are known to those skilled in the art. Preferred catalysts are phosphorus compounds, for example, sodium hypophosphite, phosphorous acid, triphenylphosphine or triphenylphosphite.

[059] The polymerization of components (A') and (B') forms at least one copolyamide which therefore comprises units derived from component (A') and units derived from component (B'). The units derived from component (B') comprise units derived from components (B1') and (B2') and optionally from component (B3').

[060] Polymerization of components (A') and (B') forms the copolyamide as a copolymer. The copolymer can be a random copolymer. It can also be a block copolymer.

[061] Formed in a block copolymer are blocks of units derived from component (B') and blocks of units derived from component (A'). These appear in alternating sequence. In a random copolymer, the units derived from component (A') alternate with units derived from component (B'). This alternation is random. For example, two units derived from component (B') may be followed by a unit derived from component (A') which is followed in turn by a unit derived from component (B') and then by a unit comprising three units derived from component (A').

[062] It is preferable that at least one copolyamide be a random copolymer. Petition 870240105284, dated 10 / 12 / 2024, page 26 / 95 14 / 77

[063] The production of at least one copolyamide preferably comprises the following steps: (I) polymerize components (A') and (B') to obtain at least one first copolyamide, (II) pelletize the at least one first copolyamide obtained in step (I) to obtain at least one pelleted copolyamide, (III) extract the at least one pelleted copolyamide obtained in step (II) with water to obtain at least one extracted copolyamide, (IV) dry the at least one extracted copolyamide obtained in step (III) at a temperature (Tt) to obtain at least one copolyamide, (IV) dry the at least one extracted copolyamide obtained in step (III) at a temperature (Tt) to obtain at least one copolyamide.

[064] Polymerization in step (I) can be carried out in any reactor known to those skilled in the art. Stirred tank reactors are preferred. It is also possible to use auxiliaries known to those skilled in the art, for example, antifoaming agents such as polydimethylsiloxane (PDMS), to improve reaction management.

[065] In step (II) the at least one first copolyamide obtained in step (I) may be pelletized by any methods known to those skilled in the art, for example, continuous (strand) pelleting or submerged pelleting.

[066] Extraction in step (III) may be carried out by any methods known to those skilled in the art.

[067] During extraction in step (III), the byproducts typically formed during the polymerization of components (A') and (B') in step (I) are extracted from at least one pelleted copolyamide.

[068] In step (IV) at least one extracted copolyamide obtained in step (III) is dried. The drying processes are known by Petition 870240105284, dated 10 / 12 / 2024, page 27 / 95 15 / 77 experts in the art. According to the invention, at least one extracted copolyamide is dried at a temperature (Tt). The temperature (Tt) is preferably above the glass transition temperature (Tg(c)) of at least one copolyamide and below the melting temperature (Tm(C)) of at least one copolyamide.

[069] Drying in step (IV) is typically carried out for a period in the range of 1 to 100 hours, preferably in the range of 2 to 50 hours and especially preferably in the range of 3 to 40 hours.

[070] It is believed that drying in step (IV) further increases the molecular weight of at least one copolyamide.

[071] At least one copolyamide – without the addition of component B – typically has a glass transition temperature (Tg(C)). The glass transition temperature (Tg <c>) is, for example, in the range of 20 °C to 50 °C, preferably in the range of 23 °C to 47 °C and, especially preferably, in the range of 25 °C to 45 °C, determined in accordance with ISO 113572:2014.

[072] In the context of the present invention, the glass transition temperature (Tg(C)) of at least one copolyamide is based, according to ISO 11357-2:2014, on the glass transition temperature (Tg(c)) of the dry copolyamide.

[073] In the context of the present invention, "dry" should be understood to mean that at least one copolyamide comprises less than 1% by weight, preferably less than 0.5% by weight and especially preferably less than 0.1% by weight of water based on the total weight of at least one copolyamide. The term "dry" should be understood more preferably to mean that at least one copolyamide does not comprise water and more preferably that at least one copolyamide does not comprise solvent. Petition 870240105284, dated 10 / 12 / 2024, p. 28 / 95 16 / 77

[074] In addition, at least one copolyamide typically has a melting temperature (Tm(C)). The melting temperature (Tm <c>) of at least one copolyamide is, for example, in the range of 150 to 210 °C, preferably in the range of 160 to 205 °C and especially preferably in the range of 160 to 200 °C, determined in accordance with ISO 11357-3:2014.

[075] At least one copolyamide generally has a viscosity index (VN(c)) in the range of 150 to 300 mL / g determined in a 0.5% by weight solution of at least one copolyamide in a phenol / odichlorobenzene mixture in a 1:1 weight ratio.

[076] It is preferable when the viscosity index (VN(c)) of at least one copolyamide is in the range of 160 to 290 mL / g, particularly preferably in the range of 170 to 280 mL / g, determined in a 0.5% by weight solution of at least one copolyamide in a phenol / dichlorobenzene mixture in a weight ratio of 1:1. Component (A')

[077] According to the invention, component (A') is at least one lactam.

[078] In the context of the present invention, "at least one lactam" is understood to mean precisely one lactam or a mixture of 2 or more lactams.

[079] Lactams are known per se by those skilled in the art. Lactams with 4 to 12 carbon atoms are preferred according to the invention.

[080] In the context of the present invention, "lactams" should be understood as meaning cyclic amides preferably having 4 to 12 carbon atoms, particularly preferably 5 to 8 carbon atoms, in the ring.

[081] Suitable lactams are, for example, those Petition 870240105284, dated 10 / 12 / 2024, p. 29 / 95 17 / 77 selected from the group consisting of 3-aminopropanolactam (propio3-lactam; β-lactam; β-propiolactam), 4-aminobutanolactam (butyro-4-lactam; γ-lactam; γ-butyrolactam), aminopentanolactam (2-piperidinone; δ-lactam; δ-valerolactam), 6-aminohexanolactam (hexane-6-lactam; ε-lactam; ε-caprolactam), 7-aminoheptanolactam (heptane-7-lactam; ζ-lactam; ζ-heptanolactam), 8-amino-octanolactam (octane-8-lactam; η-lactam; η-octanolactam), 9-aminononanolactam (nonane-9-lactam; θ-lactam; θ-nonanolactam), 10-aminodecanolactam (decane-10-lactam; ωdecanolactam), 11-aminoundecanolactam (undecane-11-lactam; ωundecanolactam) and 12-aminododecanolactam (dodecane-12-lactam; ωdodecanolactam).

[082] The present invention, therefore, also provides a process in which component A') is selected from the group consisting of 3-aminopropanolactam, 4-aminobutanolactam, 5-aminopentanolactam, 6-aminohexanolactam, 7-aminoheptanolactam, 8-aminooctanolactam, 9-aminononanolactam, 10-aminodecanolactam, 11-aminoundecanolactam and 12-aminododecanolactam.

[083] Lactams may be unsubstituted or at least monosubstituted. If at least monosubstituted lactams are used, the nitrogen atom and / or the carbon atoms of the ring thereof may contain one, two or more substituents selected independently of each other from the group consisting of C1 to C10 alkyl, C5 to C6 cycloalkyl, and C5 to C10 aryl.

[084] Suitable C1 to C10 alkyl substituents are, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl and tert-butyl. A suitable C5 to C6 cycloalkyl substituent is, for example, cyclohexyl. Preferred C5 to C10 aryl substituents are phenyl or anthranyl.

[085] It is preferable to use unsubstituted lactams, being Petition 870240105284, dated 10 / 12 / 2024, p. 30 / 95 18 / 77 preferred γ-lactam (γ-butyrolactam), δ-lactam (δ-valerolactam) and ε-lactam (ε-caprolactam). Particular preference is given to δ-lactam (δ-valerolactam) and ε-lactam (ε-caprolactam), with ε-caprolactam being especially preferred. Monomer Mixture (M)

[086] According to the invention, component (B') is a mixture of monomers (M). The mixture of monomers (M) comprises components (B1'), at least one C32-C40 dimeric acid and (B2'), at least one C4-C12 diamine.

[087] In the context of the present invention, a mixture of monomers (M) should be understood as meaning a mixture of two or more monomers, wherein at least components (B1') and (B2') are present in the mixture of monomers (M).

[088] In the context of the present invention, the terms "component (B1')" and "at least one C32-C40 dimeric acid" are used synonymously and therefore have the same meaning. The same applies to the terms "component (B2')" and "at least one C4-C12 diamine". These terms are also used synonymously in the context of the present invention and therefore have the same meaning.

[089] The monomer mixture (M) comprises, for example, in the range of 45 to 55 mol% (mol%) of component (B1') and in the range of 45 to 55 mol% of component (B2') in each case based on the sum of the molar percentages of components (B1') and (B2'), preferably based on the total amount of substance of the monomer mixture (M).

[090] It is preferable when component (B') comprises in the range of 47 to 53 mol% of component (B1') and in the range of 47 to 53 mol% of component (B2') in each case based on the sum of the mol percentages of components (B1') and (B2'), preferably based on the total amount of Petition 870240105284, dated 10 / 12 / 2024, page 31 / 95 19 / 77 substance of component B').

[091] It is particularly preferable when component (B') comprises in the range of 49 to 51 mol% of component (B1') and in the range of 49 to 51 mol% of component (B2') in each case based on the total sum of the molar percents of components (B1') and (B2'), preferably based on the total amount of substance of component (B').

[092] The mole percentages (mol%) of components (B1') and (B2') present in component (B') typically add up to 100% by mole.

[093] Component (B') may additionally comprise a component (B3'), at least one C4-C20 diacid.

[094] In the context of the present invention, the terms "component (B3')" and "at least one C4-C20 diacid" are used synonymously and therefore have the same meaning.

[095] When component (B') additionally comprises component (B3'), it is preferable that component (B') comprises in the range of 25 to 54.9 mol% of component (B1'), in the range of 45 to 55 mol% of component (B2') and in the range of 0.1 to 25 mol% of component (B3'), in each case based on the total amount of substance of component (B').

[096] It is particularly preferable when component (B') comprises in the range of 13 to 52.9 mol% of component (B1'), in the range of 47 to 53 mol% of component (B2') and in the range of 0.1 to 13 mol% of component (B3'), in each case based on the total amount of substance of component (B').

[097] It is more preferable when component (B') comprises in the range of 7 to 50.9 mol% of component (B1'), in the range of 49 to 51 mol% of component (B2') and in the range of 0.1 to 7 mol% of component (B3'), in each case based on the total amount of substance of component (B').

[098] When component (B') additionally comprises Petition 870240105284, dated 10 / 12 / 2024, page 32 / 95 20 / 77 component B3'), the molar percentages of components (B1'), (B2') and (B3') typically add up to 100% by mole.

[099] The mixture of monomers (M) may additionally comprise water.

[100] Components (B1') and (B2') and optionally (B3') of component (B') can react with each other to obtain amides. This reaction is known per se to those skilled in the art. Component (B') can therefore comprise components (B1'), (B2') and optionally (B3') in fully reacted form, partially reacted form or unreacted form. It is preferable when component (B') comprises components (B1'), (B2') and optionally (B3') in unreacted form.

[101] In the context of the present invention, the expression "in unreacted form" should be understood as meaning that component (B1') is present as at least one C32-C40 dimeric acid and component (B2') is present as at least one C4-C12 diamine and, optionally, component (B3') is present as at least one C4-C20 diacid.

[102] Thus, if components (B1') and (B2') and optionally (B3') have reacted at least partially, components (B1') and (B2') and any (B3') are at least partially in amide form. Component B1')

[103] According to the invention, component (B1') is at least a C32-C40 dimeric acid.

[104] In the context of the present invention, "at least one C32-C40 dimeric acid" should be understood as meaning precisely a C32-C40 dimeric acid or a mixture of two or more C32-C40 dimeric acids.

[105] Dimeric acids are also called dimeric fatty acids. C32-C40 dimeric acids are intrinsically known to those skilled in the art and are typically produced by dimerization of Petition 870240105284, dated 10 / 12 / 2024, p. 33 / 95 21 / 77 unsaturated fatty acids. This dimerization can be catalyzed, for example, by clay soils.

[106] Unsaturated fatty acids suitable for the production of at least one C32-C40 dimeric acid are known to those skilled in the art and are, for example, C16 unsaturated fatty acids, C18 unsaturated fatty acids and C20 unsaturated fatty acids.

[107] It is therefore preferable that component B1' be produced with unsaturated fatty acids selected from the group consisting of C16 unsaturated fatty acids, C18 unsaturated fatty acids and C20 unsaturated fatty acids, where C18 unsaturated fatty acids are particularly preferred.

[108] The appropriate unsaturated C16 fatty acid is, for example, palmitoleic acid ((9Z)-hexadeca-9-enoic acid).

[109] Suitable C18 unsaturated fatty acids are, for example, selected from the group consisting of petroselic acid ((6Z)-octadeca-6-enoic acid), oleic acid ((9Z)-octadeca-9-enoic acid), elaidic acid ((9E)-octadeca-9-enoic acid), vaccenic acid ((11E)-octadeca11-enoic acid), linoleic acid ((9Z,12Z)-octadeca-9,12-dienoic acid), α-linolenic acid ((9Z,12Z,15Z)-octadeca-9,12,15-trienoic acid), γ-linolenic acid ((6Z,9Z,12Z)-octadeca-6,9,12-trienoic acid), calendulic acid ( (8E,10E,12Z)-octadeca-8,10,12-trienoic acid), punicic acid ((9Z,11E,13Z)octadeca-9,11,13-trienoic acid), α-eleostearic acid ((9Z,11E,13E)-octadeca-9,11,13-trienoic acid) and β-eleostearic acid ((9E,11E,13E)-octadeca-9,11,13trienoic acid).Specific preference is given to unsaturated C18 fatty acids selected from the group consisting of petroselic acid ((6Z)octadeca-6-enoic acid), oleic acid ((9Z)-octadeca-9-enoic acid), elaidic acid ((9E)-octadeca-9-enoic acid), vaccenic acid ((11E)-octadeca-11-enoic acid) and linoleic acid ((9Z,12Z)-octadeca-9,12-dienoic acid). Petition 870240105284, dated 10 / 12 / 2024, page 34 / 95 22 / 77

[110] Suitable unsaturated C20 fatty acids are, for example, selected from the group consisting of gadoleic acid ((9Z)-eicosa-9-enoic acid), eicosenoic acid ((11Z)-eicosa-11-enoic acid),

[111] arachidonic acid ((5Z,8Z,11Z,14Z)-eicosa5,8,11,14-tetraenoic acid) and thymnodonic acid ((5Z,8Z,11Z,14Z,17Z)-eicosa5,8,11,14,17-pentaenoic acid).

[112] Component B1' is, especially preferably, at least one C36 dimeric acid.

[113] At least one C36 dimeric acid is preferably produced from unsaturated C18 fatty acids. It is particularly preferred that the C36 dimeric acid be produced from: C18 fatty acids selected from the group consisting of petroselic acid ((6Z)-octadeca-6-enoic acid), oleic acid ((9Z)octadeca-9-enoic acid), elaidic acid ((9E)-octadeca-9-enoic acid), vaccenic acid ((11E)-octadeca-11-enoic acid) and linoleic acid ((9Z,12Z)octadeca-9,12-dienoic acid).

[114] The production of component (B1') from unsaturated fatty acids can also form trimeric acids and unconverted unsaturated fatty acid residues can also remain.

[115] The formation of trimeric acids is known to those skilled in the art.

[116] According to the present invention, component (B1') preferably comprises no more than 0.5% by weight of unreacted unsaturated fatty acid and no more than 0.5% by weight of trimeric acid, more specifically no more than 0.2% by weight of unreacted unsaturated fatty acid and no more than 0.2% by weight of trimeric acid, in each case based on the total weight of component (B1').

[117] Dimeric acids (also known as acids Petition 870240105284, dated 10 / 12 / 2024, p. 35 / 95 23 / 77 dimerized fatty acids or dimeric fatty acids) should therefore be understood as generally, and especially in the context of the present invention, indicating mixtures produced by the oligomerization of unsaturated fatty acids. They can be produced, for example, by the catalytic dimerization of unsaturated fatty acids of vegetable origin, wherein the starting materials employed are particularly C16 to C20 unsaturated fatty acids. The linkage is mainly processed by means of the Diels-Alder mechanism and results, depending on the number and position of the double bonds in the fatty acids used to produce the dimeric acids, in mixtures of mainly dimeric products containing cycloaliphatic, linear aliphatic, branched aliphatic groups and also C6 aromatic hydrocarbons between the carboxyl groups.Depending on the mechanism and / or subsequent hydrogenation, aliphatic radicals may be saturated or unsaturated, and the proportion of aromatic groups may also vary. The radicals between the carboxylic acid groups comprise, for example, 32 to 40 carbon atoms. Production preferentially employs fatty acids containing 18 carbon atoms, so that the dimeric product therefore contains 36 carbon atoms. The radicals linking the carboxyl groups of dimeric fatty acids preferably do not comprise unsaturated bonds and aromatic hydrocarbon radicals.

[118] In the context of the present invention, production preferably employs C18 fatty acids. It is particularly preferable to employ linolenic, linoleic and / or oleic acid.

[119] Depending on the reaction management, the oligomerization described above generates mixtures comprising mainly dimeric molecules, but also trimeric molecules, as well as monomeric molecules and other byproducts. Purification by distillation is customary. Commercial dimeric acids generally comprise at least 80% by weight of Petition 870240105284, dated 10 / 12 / 2024, page 36 / 95 24 / 77 dimeric molecules, up to 19% by weight of trimeric molecules and a maximum of 1% by weight of monomeric molecules and other by-products.

[120] It is preferable to use dimeric acids consisting of at least 90% by weight, preferably at least 95% by weight, and particularly preferably at least 98% by weight of dimeric fatty acid molecules.

[121] The proportions of monomeric, dimeric and trimeric molecules and other by-products in dimeric acids can be determined, for example, by gas chromatography (GC). Dimeric acids are converted into the corresponding methyl esters by the boron trifluoride method (see DIN EN ISO 5509) before GC analysis and then analyzed by GC.

[122] In the context of the present invention, it is therefore a fundamental characteristic of "dimeric acids" that their production comprises the oligomerization of unsaturated fatty acids. This oligomerization predominantly forms, i.e., preferably up to at least 80% by weight, specifically at least 90% by weight, very specifically at least 95% by weight and, particularly, at least 98% by weight of dimeric products. The fact that the oligomerization predominantly forms dimeric products comprising precisely two fatty acid molecules justifies this designation which, in any case, is common. An alternative expression for the relevant term "dimeric acids" is therefore the term "mixture comprising dimerized fatty acids".

[123] The dimeric acids to be used can be obtained in the form of commercial products. Examples include Radiacid 0970, Radiacid 0971, Radiacid 0972, Radiacid 0975, Radiacid 0976 and Radiacid 0977 from Oleon, Pripol 1006, Pripol 1009, Pripol 1012 and Pripol 1013 from Croda, Empol 1008, Empol Petition 870240105284, dated 10 / 12 / 2024, page 37 / 95 25 / 77 1012, Empol 1061 and Empol 1062 from BASF SE and Unidyme 10 and Unidyme TL from Arizona Chemical.

[124] Component (B1') has an acidity index, for example, in the range of 190 to 200 mg KOH / g. Component B2')

[125] According to the invention, component (B2') is at least one C4-C12 diamine.

[126] In the context of the present invention, "at least one C4-C12 diamine" should be understood as referring precisely to a C4-C12 diamine or a mixture of two or more C4-C12 diamines.

[127] In the context of the present compound, "C4-C12 diamine" should be understood as indicating aliphatic and / or aromatic compounds containing from four to twelve carbon atoms and two amino groups (-NH2 groups). Aliphatic and / or aromatic compounds may be unsubstituted or, additionally, at least monosubstituted. If the aliphatic and / or aromatic compounds are additionally at least monosubstituted, they may contain one, two or more substituents that do not participate in the polymerization of components (A') and (B'). These substituents are, for example, alkyl or cycloalkyl substituents. They are known per se to those skilled in the art. At least one C4-C12 diamine is preferably unsubstituted.

[128] The appropriate B2') components are selected, for example, from the group consisting of 1,4-diaminobutane (butane-1,4-diamine; tetramethylenediamine; putrescine), 1,5-diaminopentane (pentamethylenediamine; pentane-1,5-diamine; cadaverine), 1,6-diaminohexane (hexamethylenediamine; hexane-1,6-diamine), 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane (decamethylenediamine), 1,11-diaminondecane (undecamethylenediamine) and 1,12-diaminododecane (dodecamethylenediamine). Petition 870240105284, dated 10 / 12 / 2024, page 38 / 95 26 / 77

[129] It is preferable that component (B2') be selected from the group consisting of tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, decamethylenediamine and dodecamethylenediamine. Component B3')

[130] According to the present invention, the component (B3') optionally present in component (B') is at least a C4-C20 diacid.

[131] In the context of the present invention, the expression "at least one C4-C20 diacid" should be understood as indicating precisely a C4-C20 diacid or a mixture of two or more C4-C20 diacids.

[132] In the context of the present invention, "C4-C20 diacid" should be understood to mean aliphatic and / or aromatic compounds containing from two to eighteen carbon atoms and two carboxyl groups (-COOH groups). The aliphatic and / or aromatic compounds may be unsubstituted or, additionally, at least monosubstituted. If the aliphatic and / or aromatic compounds are additionally at least monosubstituted, they may contain one, two or more substituents that do not participate in the polymerization of components (A') and (B'). These substituents are, for example, alkyl or cycloalkyl substituents. They are known to those skilled in the art. Preferably, at least one C4-C20 diacid is 'unsubstituted'.

[133] The appropriate components (B3') are selected, for example, from the group consisting of butanedioic acid (succinic acid), pentanedioic acid (glutaric acid), hexanedioic acid (adipic acid), heptanedioic acid (pimelic acid), octanedioic acid (suberic acid), nonanedioic acid (azelaic acid), decanodioic acid (sebacic acid), undecanodioic acid, dodecanodioic acid, tridecanodioic acid, tetradecanodioic acid and hexadecanodioic acid.

[134] It is preferable that the component (B3') be selected from Petition 870240105284, dated 10 / 12 / 2024, page 39 / 95 27 / 77 of the group consisting of pentanedioic acid (glutaric acid), hexanedioic acid (adipic acid), decanedioic acid (sebacic acid) and dodecanedioic acid.

[135] It is particularly preferable that component (C) be PA6 / 6.36, preferably with a melting point of 190 to 210 °C, specifically with a melting point between 195 to 200 °C, more specifically 196 to 199 °C, and / or a caprolactam (polymerized) content of 60 to 80% by weight, more preferably 65 to 75% by weight, specifically 67 to 70% by weight, wherein the remainder are PA 6.36 units derived from hexamethylene diamine and C36 diacid.

[136] As component B, the molding compositions of the invention comprise 0.1 to 10% by weight, preferably 0.5 to 5% by weight, more preferably 1 to 4% by weight of at least one plasticizer of the general formula (1). R1-O-(CH2CH2-O-)nR2 (1) with n = 1 to 10 R1, R2 being, independently, H, C1-12 alkyl, phenyl or tolyl, with a boiling point above 250 °C.

[137] Preferably, component B has a boiling point of at least 290 °C, more preferably at least 300 °C.

[138] Component B is based on ethylene glycol or polyethylene glycols. In formula (1) above, the numeral n can have any value in the range of 1 to 10, preferably 1 to 5, more preferably 3 to 5, most preferably 3.8 to 4.2.

[139] In another example of implementation, in formula (1) above, the numeral n is from 1 to 4.

[140] When a single compound of general formula (1) is used, n is an integer. When mixtures of different compounds are used Petition 870240105284, dated 10 / 12 / 2024, page 40 / 95 28 / 77 compounds of general formula (1) with different values ​​for n, n denotes the numerical average value of the ethylene glycol units contained in the compound. In this case, n can be any number in the range of 1 to 10, preferably 1 to 5, more preferably 3 to 5, most preferably 3.8 to 4.2. For example, the plasticizer can be a mixture of compounds of general formula (1) with n = 3, n = 4 and n = 5.

[141] In another example of implementation, in formula (1) above, the numeral n is from 1 to 4.

[142] More preferably, the plasticizer of general formula (1) is based on triethylene glycol, tetraethylene glycol, pentaethylene glycol or mixtures thereof. Tetraethylene glycol is most preferred. Therefore, n most preferably has a value of 3.8 to 4.2, most preferably 4.

[143] Ethylene glycol or polyethylene glycol may have one or two terminal hydroxyl groups. It is also possible that one or both hydroxyl groups are capped with ether groups. In this case, Ri and R2 are independently C1-12 alkyl, phenyl or tolyl. More preferred are C18 alkyl, specifically C1-3 alkyl. In the most preferred case, Ri and R2 are hydrogen.

[144] In another embodiment, the plasticizer of general formula (1) has a molecular weight of less than 200 g / mol, preferably less than 195 g / mol.

[145] The most preferred single compound used as a plasticizer is tetraethylene glycol which has the formula HO-(CH2CH2-O-)4H, with a molecular weight of 194.23 g / mol and a boiling point of 327 °C.

[146] Tetraethylene glycol can be used in a mixture with triethylene glycol and / or pentaethylene glycol. Therefore, n is preferably from 3.8 to 4.2.

[147] Tetraethylene glycol is non-toxic and has high plasticizing efficiency. When compared with sulfonamides and lactams, it is only half Petition 870240105284, dated 10 / 12 / 2024, page 41 / 95 29 / 77 of the amount of tetraethylene glycol is needed to obtain the same plasticizing effect and the same decrease in glass transition temperature.

[148] Therefore, the plasticizers of component B can be used in significantly smaller quantities than the plasticizers known as N-(2-hydroxypropyl)benzenesulfonamide and caprolactam or lauryl-lactam.

[149] Component B compounds are highly efficient at reducing the modulus of elasticity of molds made from thermoplastic molding composition.

[150] More preferably, the amount of component B is 1 to 5% by weight, for example, 1 to 4% by weight or 2 to 5% by weight. If the amount is 2 to 5% by weight, the maximum amount of component A is 98% by weight.

[151] As component C, the molding compositions of the present invention may comprise 0 to 45% by weight, preferably 0 to 40% by weight of at least one elastomeric polymer.

[152] If the elastic polymer is present, the minimum quantity is preferably 1% by weight, more preferably 2% by weight, most preferably 5% by weight. Thus, if the elastomeric polymer of component C is present in the molding compositions, the quantity is preferably 1 to 45% by weight, more preferably 2 to 40% by weight, most preferably 5 to 40% by weight. In this case, the maximum content of component A is reduced by the minimum content of component C.

[153] Component C can be selected from any elastomeric polymers, impact modifiers, elastomers or rubbers that are suitable for polyamide molding compositions.

[154] Preferably, component C is selected from: b1) ethylene copolymers with at least one comonomer Petition 870240105284, dated 10 / 12 / 2024, page 42 / 95 30 / 77 selected from, C3-12 olefins, C1-12 alkyl (meth)acrylates, (meth)acrylic acid and maleic anhydride as component (B1), (B2) polyethylene or polypropylene as component (B2), wherein components (B1) and (B2) may also be additionally grafted with maleic anhydride, preferably from ethylene-propylene rubbers, ethylene-propylene-diene rubbers, ethylene-butylacrylate copolymers, ethylene and / or propylene and maleic anhydride copolymers and mixtures thereof.

[155] These elastomeric polymers (also called impact modifiers, elastomers or rubbers) are 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.

[156] Polymers of this type are described, for example, in Houben-Weyl, Methoden der organischen Chemie, Vol. 14 / 1 (Georg-ThiemeVerlag, Stuttgart, Germany, 1961), pages 392-406 and in the monograph by CB Bucknall, "Toughened Plastics" (Applied Science Publishers, London, United Kingdom, 1977).

[157] Some preferred types of such elastomers are described below.

[158] The preferred types of such elastomers are those known as ethylene-propylene (EPM) and ethylene-propylene-diene (EPDM) rubbers.

[159] EPM rubbers generally have virtually no residual double bonds, whereas EPDM rubbers can have from 1 to 20 double bonds per 100 carbon atoms. Petition 870240105284, dated 10 / 12 / 2024, page 43 / 95 31 / 77

[160] Examples of diene monomers for EPDM rubbers that may be mentioned are conjugated dienes, such as isoprene and butadiene, non-conjugated dienes having from 5 to 25 carbon atoms, such as 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 2,5-dimethyl-1,5-hexadiene and 1,4-octadiene, cyclic dienes, such as cyclopentadiene, cyclohexadienes, cyclooctadienes and dicyclopentadiene, and also alkenylnorbornenes, such as 5-ethylidene-2-norbornene, 5-butylidene-2-norbornene, 2-metalyl-5-norbornene and 2-isopropenyl-5-norbornene, and tricyclodienes, such as 3-methyltricyclo[5.2.1.02,6]-3,8-decadiene and mixtures thereof. Preference is given to 1,5-hexadiene, 5-ethylidenonorbornene and dicyclopentadiene. The diene content of EPDM rubbers is preferably from 0.5 to 50% by weight, in particular from 1 to 8% by weight, based on the total weight of the rubber.

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

[162] Copolymers of ethylene with acrylic acid and / or methacrylic acid and / or with esters of these acids are another preferred group of rubbers. Rubbers may also comprise dicarboxylic acids, such as maleic acid and fumaric acid, or derivatives of these acids, for example, esters and anhydrides, and / or monomers comprising epoxy groups. These monomers comprising derivatives of dicarboxylic acids or comprising epoxy groups are preferably incorporated into the rubber by adding to the monomer a mixture of monomers comprising dicarboxylic acid groups and / or epoxy groups and having a general formula I or II or III or IV. Petition 870240105284, dated 10 / 12 / 2024, page 44 / 95 32 / 77 R1C(COOR2)=C(COOR3)R4(I)R\ / R4cc II(ll) occo o / °\ CHR7= CH (CH2)m O —(CHR8)g—CH CHR5C) CH2= CR9COO (CH2)pCH—CHR8(IV) In which R1 to R9 are hydrogen or alkyl groups that have 1 to 6 carbon atoms, g is an integer from 0 to 20, g is an integer from 0 to 10, and p is an integer from 0 to 5.

[163] The radicals R1a R9 are preferably hydrogen, where m is 0 or 1 and g is 1. The corresponding compounds are maleic acid, fumaric acid, maleic anhydride, allyl glycidyl ether and vinyl glycidyl ether.

[164] Preferred compounds of formulas I, II and IV are maleic acid, maleic anhydride and (meth)acrylates comprising epoxy groups, such as glycidyl acrylate and glycidyl methacrylate, and esters with tertiary alcohols, such as tert-butyl acrylate. Although the latter does not have free carboxy groups, its behavior approaches that of free acids and, therefore, they are called monomers with latent carboxy groups.

[165] Copolymers are advantageously composed of 50 to 98% by weight of ethylene, 0.1 to 20% by weight of monomers comprising epoxy and / or methacrylic acid groups and / or monomers comprising anhydride groups, the remaining amount being (meth)acrylates.

[166] Special preference is given to copolymers composed of: 50 to 98% by weight, in particular 55 to 95% by weight of ethylene, 0.1 to 40% by weight, in particular 0.3 to 20% by weight Petition 870240105284, dated 10 / 12 / 2024, page 45 / 95 33 / 77 of glycidyl acrylate and / or glycidyl methacrylate, (meth)acrylic acid and / or maleic anhydride, and - from 1 to 45% by weight, in particular from 5 to 40% by weight of n-butyl acrylate and / or 2-ethylhexyl acrylate.

[167] Other preferred (meth)acrylates are methyl, ethyl, propyl, isobutyl and tert-butyl ethers.

[168] Comonomers that can be used alongside them are vinyl esters and vinyl ethers.

[169] The ethylene copolymers previously described can be prepared by processes known per se, preferably by random copolymerization at high pressure and high temperature. The appropriate processes are well known.

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

[171] In principle, it is possible to use homogeneously structured elastomers or those with a shell structure. The shell-like 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.

[172] The monomers that may be mentioned here, simply as examples, for the preparation of the rubber fraction of elastomers are acrylates, such as n-butyl acrylate and 2-ethylhexyl acrylate, corresponding methacrylates, butadiene and isoprene, and also mixtures thereof. These monomers may be copolymerized with other monomers, such as styrene, acrylonitrile, vinyl ethers, and with other acrylates or methacrylates, such as methyl methacrylate, methyl acrylate, ethyl acrylate, or acrylate of Petition 870240105284, dated 10 / 12 / 2024, page 46 / 95 34 / 77 propyl.

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

[174] If one or more hard components (with glass transition temperatures above 20 °C) are involved in addition to the rubber phase in the elastomer structure, these are generally prepared by polymerization, with styrene, acrylonitrile, methacrylonitrile, α-methylstyrene, p-methylstyrene or acrylates or methacrylates, such as methyl acrylate, ethyl acrylate or methyl methacrylate, as the main monomers. In addition to these, it is also possible to use relatively small proportions of other comonomers.

[175] In some cases, it has proven advantageous to use emulsion polymers that have reactive groups on their surfaces. Examples of such groups are epoxy, carboxy, latent carboxy, amino and amide groups, and also functional groups that can be introduced by the concomitant use of monomers of general formula: R10R I1.-2 CH = C--X—N--CR2II The substituents can be defined as follows: R10 is hydrogen or a C1-C4 alkyl group, R11 is hydrogen, a C1-C8 alkyl group or an aryl group, in particular phenyl, R12 is hydrogen, a C1-C10 alkyl group, a C6-C12 aryl group, or -OR13. Petition 870240105284, dated 10 / 12 / 2024, page 47 / 95 35 / 77 R13 is a C1-C8 alkyl group or a C6-C12 aryl group, which may optionally be substituted by groups comprising O or by groups comprising N. X is a chemical bond, a C1-C10 alkylene group or a C6-C12 arylene group, or II — C —Y Y is OZ or NH-Z, and Z is a C1-C10 alkylene or C6-C12 arylene group.

[176] The graft monomers described in EP-A document 208 187 are also suitable for introducing reactive groups onto the surface.

[177] Other examples that may be mentioned are acrylamide, methacrylamide and acrylates or substituted methacrylates, such as (N-tert-butylamino)ethyl methacrylate, (N,N-dimethylamino)ethyl acrylate, (N,N-dimethylamino)methyl acrylate and (N,N-diethylamino)ethyl acrylate.

[178] The rubber phase particles may also have been crosslinked. Examples of crosslinking monomers are 1,3-butadiene, divinylbenzene, diallyl phthalate and dihydrodicyclopentadienyl acrylate, and also the compounds described in EP-A 50 265 document.

[179] It is also possible to use monomers known as graft-link monomers, that is, monomers with two or more polymerizable double bonds that react at different rates during polymerization. Preference is given to the use of compounds of this type in which at least one reactive group polymerizes at approximately the same rate as the other monomers, while the other reactive group (or groups), for example, polymerize(s) significantly more slowly. The different polymerization rates give rise to a certain proportion of unsaturated double bonds in Petition 870240105284, dated 10 / 12 / 2024, page 48 / 95 36 / 77 rubber. If another phase is then grafted onto a rubber of this type, at least some of the double bonds present in the rubber react with the monomers of the graft to form chemical bonds, that is, the grafted phase has at least some degree of chemical bonding to the base graft.

[180] Examples of graft-link monomers of this type are monomers comprising allyl groups, in particular allyl esters of ethylenically unsaturated carboxylic acids, for example, allyl acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate and diallyl itaconate, and the corresponding monoallyl compound of these dicarboxylic acids. In addition to these, there is a wide variety of other suitable graft-link monomers. For more details, reference may be made, for example, to US patent 4,148,846.

[181] The proportion of these crosslinking monomers in the impact modifier polymer is generally up to 5% by weight, preferably not more than 3% by weight, based on the impact modifier polymer.

[182] Some preferred emulsion polymers are listed below. First, mention may be made of graft polymers with a core and at least one outer shell, having the following structure: Type Monomers for the core Monomers for the envelope I 1,3-butadiene, isoprene, n-butyl acrylate, ethylhexyl acrylate or a mixture thereof styrene, acrylonitrile, methyl methylate II as I, but with concomitant use of crosslinking agents as I III as I or II n-butyl acrylate, ethyl acrylate, methyl acrylate, 1,3-butadiene, isoprene, ethylhexyl acrylate IV as I or II as I or III, but with concomitant use of monomers that have reactive groups, as described herein V styrene, acrylonitrile, methyl methacrylate or a mixture thereof first envelope composed of monomers as described in I and II for the core, the second envelope as described in I or IV for the shell

[183] ​​Instead of graft polymers whose structure has more of Petition 870240105284, dated 10 / 12 / 2024, page 49 / 95 37 / 77 In addition to a shell, it is also possible to use homogeneous elastomers, i.e., simple shells, composed of 1,3-butadiene, isoprene and n-butyl acrylate or copolymers thereof. These products can also be prepared by the concomitant use of crosslinking monomers or monomers that have reactive groups.

[184] Examples of preferred emulsion polymers are n-butyl acrylate / (meth)acrylic acid copolymers, n-butyl acrylate / glycidyl acrylate or n-butyl acrylate / glycidyl methacrylate copolymers, graft polymers with an inner core composed of n-butyl acrylate or butadiene-based and with a shell composed of the copolymers mentioned above, and ethylene copolymers with comonomers providing reactive groups.

[185] The elastomers described can also be prepared by other conventional processes, for example, by suspension polymerization.

[186] Silicone rubbers are also preferred, as described in documents DE-A 37 25 576, EP-A 235 690, DE-A 38 00 603 and EP-A 319 290.

[187] Obviously, it is also possible to use mixtures of the types of rubber mentioned above.

[188] Preferably the elastomer is selected from: b1) ethylene copolymers with at least one comonomer selected from C3-12 olefins, C1-12 alkyl (meth)acrylates, (meth)acrylic acid, maleic anhydride, as component B1), b2) polyethylene or polypropylene as component B2), wherein components B1) and B2) may also be additionally grafted with maleic anhydride.

[189] Component B1) may comprise one or more Petition 870240105284, dated 10 / 12 / 2024, page 50 / 95 38 / 77 different comonomers, preferably 1 to 3 different copolymers, particularly preferably one or two different comonomers. The C3-12 olefins are preferably linear, terminal C3-12 olefins, particularly preferably C3-8 olefins. Examples of suitable olefins are propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene and 1-octene.

[190] According to one embodiment, component B) is not polyethylene. According to one embodiment of the invention, component B2) is not polyethylene. However, in this embodiment, component B2) may be polyethylene grafted with maleic anhydride. It is also possible to employ mixtures of polyethylene with the other elastomers mentioned as components B1) and B2).

[191] C1-12 alkyl (meth)acrylates comprise C1-12 alkyl radicals, preferably C2-6 alkyl radicals, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, ethylhexyl radicals. Alkyl acrylates are preferably relevant.

[192] In copolymers of component B1) the proportion of ethylene base units is preferably 1% to 99% by weight, particularly preferably 60% to 98% by weight, especially preferably 84% to 96% by weight.

[193] The following preferred quantities apply to comonomers: C3-12 olefins: preferably 99% to 1% by weight, particularly preferably 40% to 10% by weight; C1-12 alkyl (meth)acrylates: preferably 40% to 2% by weight, particularly preferably 30% to 5% by weight. (Meth)acrylic acid: preferably 40% to 2% by weight, particularly preferably 30% to 5% by weight, Maleic anhydride: preferably 3% to 0.01% by weight, Petition 870240105284, dated 10 / 12 / 2024, page 51 / 95 39 / 77 particularly 2% to 0.1% by weight,

[194] The total amount of comonomers is preferably in the range of 1% to 99% by weight, particularly preferably from 2% to 40% by weight.

[195] Component copolymers (B1) can be random or block copolymers. The former consist of a crystallizing and therefore physically crosslinked main polymer (polyethylene) whose degree of crystallization is reduced by a comonomer randomly incorporated along the chain, so that the crystallites in the finished molding material are no longer in direct contact. They then act as isolated crosslinking points as in conventional elastomers.

[196] In block copolymers, the hard and soft segments of a molecule are highly distinct. In thermoplastic elastomers, the material separates into a continuous phase and a discontinuous phase below a certain temperature. As soon as the latter fall to a temperature below their glass temperature, they act, in turn, as a crosslinking point.

[197] The copolymer of component (B1) can also be grafted with maleic anhydride. The maleic anhydride used for grafting is preferably used in an amount of 5% to 0.005% by weight, particularly preferably from 3% to 0.01% by weight, based on the copolymer of component (B1). In the grafted copolymer of component (B1) the proportion of maleic anhydride is preferably in the range of 2% to 0.1% by weight based on the ungrafted copolymer of component (B1).

[198] Component (B1) preferably has a melt flow index (MVR) value (190 °C / 2.16 kg, according to ISO1133) of 0.1 to 20 cm3 / 10 min, and particularly preferably of 0.1 to 15 cm3 / 10 min. Petition 870240105284, dated 10 / 12 / 2024, p. 52 / 95 40 / 77

[199] Alternatively or in addition to component B1, polyethylene, polypropylene or a mixture thereof is employed as component B2. This component B2 may also be grafted with maleic anhydride, wherein the proportion of maleic anhydride based on polyolefin is 5% to 0.005% by weight, preferably 2% to 0.1% by weight.

[200] Component (B2) preferably has an MVR value (190 °C / 2.16 kg, according to ISO1133) of 0.1 to 20 cm3 / 10 min, and particularly preferably of 0.1 to 15 cm3 / 10 min.

[201] The term "elastomer" describes components B1 and B2 which may optionally be grafted with maleic anhydride. Thermoplastic elastomers (TPEs) may be preferentially relevant. At room temperature, TPE exhibits behavior comparable to classical elastomers, but is plastically deformable when heated and therefore exhibits thermoplastic behavior.

[202] Mixtures of components B1 and B2 can also be used according to the present invention. These are particularly elastomeric alloys (polymixtures).

[203] Thermoplastic elastomers are generally copolymers comprising a "soft" elastomer component and a "hard" thermoplastic component. Their properties thus lie between those of elastomers and thermoplastics.

[204] Polyolefin elastomers (POE) are polymerized, for example, through the use of metallocene catalysts, examples of which include ethylene-propylene elastomers (EPR or EPDM).

[205] The most common polyolefin elastomers are ethylene-butene or ethylene-octene copolymers.

[206] For a further description of elastomers suitable as component C), reference may also be made to US Patents Petition 870240105284, dated 10 / 12 / 2024, page 53 / 95 41 / 77 5,482,997, US 5,602,200, US 4,174,358 and WO 2005 / 014278 A1.

[207] Examples of suitable elastomers can be obtained, for example, from Lyondellbasell under the designations Lucalen A2540D and Lucalen A2700M. Lucalen A2540D is a low-density polyethylene comprising a butyl acrylate comonomer. It has a density of 0.923 g / cm3 and a Vicat softening temperature of 85 °C and a melting temperature of 103 °C at a butyl acrylate content of 6.5% by weight.

[208] Lucalen A2700D is a low-density polyethylene comprising, similarly, a butyl acrylate comonomer. It has a density of 0.924 g / cm3, a Vicat softening temperature of 60 °C and a melting temperature of 95 °C.

[209] ExxonMobil's Exxelor® VA 1801 polymer resin is a semicrystalline ethylene copolymer functionalized with maleic anhydride via reactive extrusion and has intermediate viscosity. The first polymer backbone is fully saturated. The density is 0.880 g / cm3 and the proportion of maleic anhydride is typically in the range of 0.5% to 1.0% by weight.

[210] As component D, the thermoplastic molding composition contains 0 to 60% by weight, preferably 0 to 50% by weight, more preferably 0 to 40% by weight of at least one fibrous and / or particulate filler.

[211] Preferably, component D comprises glass fibers and is present in an amount of 10 to 60% by weight, more preferably 15 to 50% by weight, most preferably 20 to 40% by weight.

[212] If component D is present, the maximum quantity of component A is reduced by the minimum quantity of component D, so that the total quantity of components A to E is still 100% in Petition 870240105284, dated 10 / 12 / 2024, page 54 / 95 42 / 77 weight.

[213] Fibrous or particulate D fillers that can be mentioned are carbon fibers, glass fibers, glass beads, amorphous silica, calcium silicate, calcium metasilicate, magnesium carbonate, kaolin, chalk, powdered quartz, mica, barium sulfate and feldspar.

[214] Preferred fibrous fillers that may be mentioned are carbon fibers, aramid fibers and potassium titanate fibers, with particular preference given to glass fibers in the form of E-glass. These may be used as wicks or in the commercially available forms of chopped glass.

[215] The fibrous fillers may have been surface pre-treated with a silane compound to improve compatibility with the thermoplastic.

[216] Suitable silane compounds have the general formula: (X— (CH2)n)k—Si-(O-CmH2m+1 )4-k where the definitions of the substituents are as follows: X NH-, CH-CH-, HO-,2V n is an integer from 2 to 10, preferably from 3 to 4, m is an integer from 1 to 5, preferably from 1 to 2; ek is an integer from 1 to 3, preferably 1.

[217] Preferred silane compounds are aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane and aminobutyltriethoxysilane and also the corresponding silanes comprising a glycidyl group as the substituent X.

[218] The amounts of silane compounds generally used for surface coating are from 0.01 to 2% by weight, preferably Petition 870240105284, dated 10 / 12 / 2024, p. 55 / 95 43 / 77 from 0.025 to 1.0% by weight and in particular from 0.05 to 0.5% by weight (based on component D).

[219] Acicular mineral fillers are also suitable.

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

[221] Other fillers that may be mentioned are kaolin, calcined kaolin, wollastonite, talc and chalk, and also lamellar or acicular nanofillers, with quantities preferably from 0.1 to 10%. Preferred materials for this purpose are boehmite, bentonite, montmorillonite, vermiculite, hectorite and laponite. The lamellar nanofillers are organically modified by methods of the prior art, to give them good compatibility with the organic binder. The addition of lamellar or acicular nanofillers to the nanocomposites of the invention gives an additional increase in mechanical strength.

[222] As component E, the molding compositions of the present invention may contain 0 to 25% by weight, preferably 0 to 20% by weight, more preferably 0 to 15% by weight of other additives.

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

[224] The thermoplastic molding compositions of the invention may comprise as component E conventional processing aids, additional stabilizers, oxidation retarders, agents to neutralize heat decomposition and ultraviolet light decomposition, lubricants and release agents, colorants, such as dyes and pigments, Petition 870240105284, dated 10 / 12 / 2024, page 56 / 95 44 / 77 nucleating agents, plasticizers, etc.

[225] The molding compositions of the invention may comprise, as component E1), from 0.05 to 3% by weight, preferably from 0.1 to 1.5% by weight, and in particular from 0.1 to 1% by weight, of a lubricant.

[226] Salts of Al, of alkali metals or of alkaline earth metals, or esters or amides of fatty acids with 10 to 44 carbon atoms, preferably with 12 to 44 carbon atoms, are preferred.

[227] The metal ions are preferably alkaline earth metal and Al, with particular preference given to Ca or Mg.

[228] Preferred metal salts are Ca stearate and Ca montanate, and also Al stearate.

[229] It is also possible to use a mixture of several salts, in any desired mixing ratio.

[230] Carboxylic acids can be monobasic or dibasic. Examples that can be mentioned are pelargonic acid, palmitic acid, lauric acid, margaric acid, dodecanedioic acid, behenic acid and, in a particularly preferred way, stearic acid, capric acid and also montanic acid (a mixture of fatty acids with 30 to 40 carbon atoms).

[231] Aliphatic alcohols can be mono- to tetra-hydric. Examples of alcohols are n-butanol, n-octanol, stearyl alcohol, ethylene glycol, propylene glycol, neopentyl glycol and pentaerythritol, with glycerol and pentaerythritol being preferred.

[232] Aliphatic amines can be mono- to tribasic. Examples of these are stearylamine, ethylenediamine, propylenediamine, hexamethylenediamine, di(6-aminohexyl)amine, with particular preference given to ethylenediamine and hexamethylenediamine. Preferred esters or amides are, correspondingly, glycerol distearate, glycerol tristearate, ethylenediamine distearate, glycerol monopalmitate, trilaurate of Petition 870240105284, dated 10 / 12 / 2024, page 57 / 95 45 / 77 glycerol, glycerol monobenate and pentaerythritol tetrastearate.

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

[234] As component (E) the molding materials according to the invention may preferably comprise from 0.01% to 3% by weight, particularly preferably from 0.02% to 2% by weight, in particular from 0.05% to 1.0% by weight, of at least one heat stabilizer based on the total weight of the composition.

[235] Heat stabilizers are preferably selected from copper compounds, secondary aromatic amines, sterically hindered phenols, phosphites, phosphonites and mixtures thereof.

[236] As component E, 0.05 to 3% by weight may be used, preferably 0.1 to 2% by weight, in particular 0.1 to 1% by weight of at least one sterically hindered phenol antioxidant.

[237] This component E preferably has a molecular weight greater than 500 g / mol, more preferably greater than 1000 g / mol. In addition, component C should preferably exhibit high thermal stability, for example, a maximum weight loss of 5%, more preferably a maximum weight loss of 2%, measured under nitrogen at 300 °C within a TGA (thermogravimetric analysis) experiment (40 °C to 120 °C at 10 °C / min, isothermal temperature after 15 min followed by 120 °C to 600 °C at 20 °C / min).

[238] Component E preferably has 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 to the structure of component E. Petition 870240105284, dated 10 / 12 / 2024, p. 58 / 95 46 / 77

[239] Suitable sterically hindered phenols E are, in principle, all compounds that have a phenolic structure and that 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.

[240] It is preferable to use, for example, compounds with the formula: R2\Ry HO- / 2 R1em que, R1 and R2 are an alkyl group, a substituted alkyl group, or a substituted triazole group, wherein the radicals R1 and R2 may be identical or different, and R3 is an alkyl group, a substituted alkyl group, an alkoxy group, or a substituted amino group. The alkyl and alkoxy residues preferably have from 1 to 12 carbon atoms, more preferably from 1 to 6 carbon atoms. The substituents are preferably C1-12 alkyl, more preferably C1-6 alkyl, most preferably C1-4 alkyl. At least one of R1 to R3 is preferably a bulky group as defined above.

[241] Antioxidants of the type mentioned above are described by way of example in document DE-A 27 02 661 (US-A 4 360 617).

[242] Another preferred group of 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 in the phenyl group. They contain at least one unit, but preferably two units, of covalently linked substituted phenylcarboxylic acid in their structures, which preferably have at least one bulky group in the phenyl group.

[243] The preferred phenylcarboxylic acids are the C1-phenyl acids Petition 870240105284, dated 10 / 12 / 2024, page 59 / 95 47 / 77 12-carboxylic acids, more preferably C2-6-phenylcarboxylic acids. The phenyl group is preferably a phenol group possessing at least one bulky group on the phenolic ring, as indicated above. Thus, the sterically hindered phenols mentioned above are preferably covalently linked to a C1-12 carboxylic alkane acid, more preferably a linear C2-6 carboxylic alkane acid.

[244] Particularly preferred compounds from this class are compounds of the formula: where R4, R5, R7 and R8, independently of each other, are C1-C8 alkyl groups that may have substitution (at least one of these being a bulky group), and R6 is a divalent aliphatic radical having from 1 to 10 carbon atoms and whose main chain may also have C-O bonds. At least one of R4 to R8 is a bulky group as defined above.

[245] The preferred compounds corresponding to these formulas are: ch.^ C chz' HOCH CH2—CH2—CO—CH—CH-O-CH—CH-O-CH—CH-OC-CH—CH. CH 'ch OH CH CH (Irganox® 245 from BASF SE) ch3,C ch3zHO CH·-... W CHf \h3ch3 CH2-CH2-CO—(CH2)6-OC-CH2-CH2— CH3^ / CH3 W 'ch3OH ^CH. C ch / \h. '3 '3 (Irganox® 259 from BASF SE) Petition 870240105284, dated 10 / 12 / 2024, page 60 / 95 48 / 77

[246] All of the following should be mentioned as examples of sterically hindered phenols: 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 1,6-hexanediol bis[3(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], pentaerythrityl tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (Irganox® 1010 from BASF SE), 3,5-di-tert-butyl-4-hydroxybenzylphosphonate distearyl, 3,5-di-tert-butyl-4-hydroxyhydrocinnamate 2,6,7-trioxa-1-phosphabicyclo[2.2.2]oct-4-ylmethia, 3,5-di-tert-butyl-4-hydroxyphenyl-3,5distearylthiotriazylamine, 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.

[247] The compounds that have been proven to be particularly effective and are therefore preferably used are 2,2'-methylenebis(4-methyl-6-tert-butylphenol), bis(3,5-di-tert-butyl-4-hydroxyphenyl]propionate of 1,6hexanediol (Irganox® 259), pentaerythrityl tetrakis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and also N,N'-hexamethylene-bis-3,5-di-tert-butyl-4-hydroxyhydrocinamide (Irganox®1098) and the Irganox®245 and Irganox®1010 products described above from BASF SE, which have particularly good compatibility.

[248] In some cases, sterically hindered phenols that have no more than one sterically hindered group in the ortho position relative to the hydroxy phenolic group have proved to be particularly advantageous; in particular when assessing color fastness during storage in diffuse light for extended periods of time.

[249] In addition, it is advantageous to employ sterically hindered phenol antioxidants that also have a sufficiently high molecular weight, preferably greater than 500 g / mol and especially a molecular weight greater than 1000 g / mol. Furthermore, they preferably exhibit a high Petition 870240105284, dated 10 / 12 / 2024, page 61 / 95 49 / 77 thermal stability measured by TGA (thermogravimetric analysis) of less than 2% degradation up to 300 °C under a nitrogen atmosphere.

[250] The molding compositions of the invention may comprise, as component E2, from 0.05 to 3% by weight, preferably from 0.1 to 1.5% by weight, and in particular from 0.1 to 1% by weight, of a copper stabilizer, preferably a Cu(I) halide, in particular in a mixture with an alkali metal halide, preferably KI, in particular in a 1:4 ratio, or a sterically hindered phenol, or a mixture thereof.

[251] The preferred monovalent copper salts used are cuprous acetate, cuprous chloride, cuprous bromide and cuprous iodide. The materials comprise these in amounts of 5 to 500 ppm of copper, preferably 10 to 250 ppm, based on polyamide.

[252] The advantageous properties are obtained in particular if copper is present with molecular distribution in the polyamide. This is achieved if a concentrate comprising the polyamide and comprising a monovalent copper salt and comprising an alkali metal halide in the form of a homogeneous solid solution is added to the molding composition. By way of example, a typical concentrate is composed of 79 to 95% by weight of polyamide and 21 to 5% by weight of a mixture composed of copper iodide or copper bromide and potassium iodide. The concentration of copper in the homogeneous solid solution is preferably 0.3 to 3% by weight, in particular 0.5 to 2% by weight, based on the total weight of the solution, and the molar ratio of cuprous iodide to potassium iodide is 1 to 11.5, preferably 1 to 5.

[253] Suitable polyamides for the concentrate are homopolyamides and copolyamides, in particular nylon-6.

[254] According to a preferred embodiment of the present invention, the molding compositions are copper-free, Petition 870240105284, dated 10 / 12 / 2024, page 62 / 95 50 / 77 specifically copper stabilizers, such as Cu(I) halides, and combinations of Cu(I) halides with alkali metal halides.

[255] More preferably, the thermoplastic molding compositions of the present invention are free of metal halides. Metal halide-free systems, so-called electrically favorable systems, are of great interest since electromobility, electrification and connectivity are a growing trend in almost all industries.

[256] Therefore, the thermoplastic molding composition is preferably free of metal halides, specifically Cu halides and alkali metal halides.

[257] The molding compositions of the invention may comprise from 0.001 to 10% by weight, preferably from 0.05 to 5% by weight, in particular from 0.1 to 2.5% by weight of iron powder with a particle size of no more than 10 µm (dsc value). The iron powder may preferably be obtained by thermal decomposition of iron pentacarbonyl.

[258] Iron occurs in some allotropes: 1. α-Fe (ferrite) forms centrally located cubic lattices, is magnetizable, dissolves a small amount of carbon, and occurs in pure iron up to 928 °C. At 770 °C (Curie temperature) it loses its ferromagnetic properties and becomes paramagnetic; iron in the temperature range of 770 to 928 °C is also called β-Fe. At normal temperature and a pressure of at least 13,000 MPa, α-Fe becomes what is known as εFe with a reduction of approximately 0.20 cm³ / mol in volume, then the density increases from 7.85 to 9.1 (at 20,000 MPa). 2. γ-Fe (austenite) forms face-centered cubic lattices, is non-magnetic, dissolves a large amount of carbon, and can only be observed in the temperature range of 928 to 1398 °C. Petition 870240105284, dated 10 / 12 / 2024, page 63 / 95 51 / 77 3. δ-Fe, centered in space, exists from 1398 °C up to its melting point of 1539 °C.

[259] Metallic iron is generally silvery white, density 7.874 (heavy metal), melting point 1539 °C, boiling point 2880 °C; specific heat (from 18 to 100 °C) approximately 0.5 g-1K-1, tensile strength from 220 to 280 N / mm2. The values ​​apply to chemically pure iron.

[260] Industrial iron production uses smelting of iron ores, iron slag, calcined pyrite or blast furnace dust and remelting of scrap and alloys.

[261] The iron powder of the invention is produced by thermal decomposition of iron pentacarbonyl, preferably at temperatures of 150 °C to 350 °C. The particles that can be obtained in this way preferably have a spherical shape, therefore being spherical or nearly spherical (another term used being spherolitic).

[262] The preferred iron powder has a particle size distribution described below and the particle size distribution in this case is determined by laser diffusion in a highly dilute aqueous suspension (e.g., using a Beckmann LS13320). The particle size (and distribution) described below can optionally be obtained by grinding and / or sieving.

[263] dxx in this case means that XX% of the total volume of the particles is less than the quoted value.

[264] d50 values: maximum 10 μm, preferably 1.6 to 8 μm, in particular 2.9 to 7.5 μm, most particularly 3.4 to 5.2 μm.

[265] d10 values: preferably from 1 to 5 μm, in particular from 1 to 3 μm and very particularly from 1.4 to 2.7 μm. Petition 870240105284, dated 10 / 12 / 2024, p. 64 / 95 52 / 77

[266] dso values: preferably from 3 to 35 μm, in particular from 3 to 12 μm and very particularly from 6.4 to 9.2 μm.

[267] The iron powder preferably has an iron content of 97 to 99.8 g / 100 g, preferably 97.5 to 99.6 g / 100 g. The content of other metals is preferably below 1000 ppm, in particular below 100 ppm and most particularly below 10 ppm.

[268] The Fe content is usually determined by infrared spectroscopy.

[269] The C content is preferably from 0.01 to 1.2 g / 100 g, preferably from 0.05 to 1.1 g / 100 g and especially from 0.4 to 1.1 g / 100 g. This C content in the preferred iron powders corresponds to powders that are not reduced with hydrogen after the thermal decomposition process.

[270] The carbon content is normally determined by burning the sample in an oxygen stream and then using IR to detect the resulting CO2 gas (using Leco CS230 or Juwe CS-mat 6250) by a method based on ASTM E1019.

[271] The nitrogen content is preferably a maximum of 1.5 g / 100 g, preferably from 0.01 to 1.2 g / 100 g.

[272] The oxygen content is preferably a maximum of 1.3 g / 100 g, preferably from 0.3 to 0.65 g / 100 g.

[273] N and O are determined by heating the specimen to around 2100 °C in a graphite furnace. The oxygen obtained from the specimen is converted to CO and measured using an IR detector. NO released under the reaction conditions of the compounds containing N is discharged with the gaseous vehicle and detected and recorded using a TCD (Thermal Conductivity Detector) (both methods being based on ASTM E1019 standard).

[274] The compacted density is preferably from 2.7 to Petition 870240105284, dated 10 / 12 / 2024, pp. 65 / 95 53 / 77 g / cm3. This generally means the density when the powder is, for example, loaded into the container and compacted by vibration. The iron powder to which preference is given may have been surface coated with iron phosphate, iron phosphite or SiO2.

[275] The BET surface area for DIN ISO 9277 is preferably from 0.1 to 10 m2 / g, in particular from 0.1 to 5 m2 / g, and preferably from 0.2 to 1 m2 / g and in particular from 0.4 to 1 m2 / g.

[276] To achieve a particularly good dispersion of the iron particles, a masterbatch involving a polymer may be used. Suitable polymers for this purpose are polyolefins, polyesters or polyamides, and it is preferred in this case that the polymer in the masterbatch be the same as component A. The mass fraction of iron in the polymer is generally 15 to 80% by weight, preferably 20 to 40% by weight.

[277] UV stabilizers that can be mentioned, the quantities of which are generally up to 2% by weight, based on the composition for molding, are various substituted resorcinols, salicylates, benzotriazoles and benzophenones. Nigrosine can also be used.

[278] 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.

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

[280] Thermoplastic molding compositions may also contain flame retardants as component E.

[281] As component E, thermoplastic molding materials may comprise 1.0 to 10.0% by weight, preferably 2.0 Petition 870240105284, dated 10 / 12 / 2024, page 66 / 95 54 / 77 to 6.0, in particular 3.0 to 5.0% by weight, of at least one phosphazene of general formula (IX) or (X) as a flame retardant.

[282] The minimum quantity of this component E is at least 1.0% by weight, preferably 2.0% by weight, in particular 3.0% by weight.

[283] The maximum amount of this component E is 10.0% by weight, preferably 6.0% by weight, particularly preferably 5.0% by weight.

[284] “Phosphazenes” should be understood as meaning cyclic phosphazenes of general formula (IX) OR4 OR4' m (IX) wherein M is an integer from 3 to 25 and R4 and R4' are identical or different and represent C1-C20 alkyl, C6-C30 aryl, C6-C30 arylalkyl or substituted C6-C30 arylalkyl or linear phosphazenes of general formula (X) OR4 OR4' (X) where n represents 3 to 1000 and X represents -N = P(OPh)3 or -N = P(O)OPh and Y represents -P(OPh)4 or -P(O)(OPh)2.

[285] The production of such phosphazenes is described in EPA document 0 945 478.

[286] Particular preference is given to cyclic phenoxyphosphazenes of formula P3N3C36 of formula (XI): Petition 870240105284, dated 10 / 12 / 2024, p. 67 / 95 55 / 77 PhO ^OPh PN^ ^N OPh OPh (XI) or linear phenoxyphosphazenes according to formula (XII) (XII)

[287] The phenyl radicals may be optionally substituted. The phosphazenes in the context of the present application are described in Mark, JE, Allcock, HR, West, R., "Inorganic Polymers", Prentice Hall, 1992, pages 61 to 141.

[288] Cyclic phenoxyphosphazenes with at least three phenoxyphosphazene units are preferably used as component E. The corresponding phenoxyphosphazenes are described, for example, in document US 2010 / 0261818 in paragraphs

[0051] to

[0053] . In particular, reference may be made to formula (I). The corresponding cyclic phenoxyphosphazenes are further described in EP-A-2 100 919, particularly in paragraphs

[0034] to

[0038] . Production may be carried out as described in document EP-A-2 100 919 in paragraph

[0041] . In an example of the invention, the phenyl groups in the cyclic phenoxyphosphazene may be replaced by C1-4 alkyl radicals. This is preferable when pure phenyl radicals are used.

[289] For a more detailed description of cyclic phosphazenes, reference may be made to Rompp Chemie Lexikon, 9th Ed., keyword "phosphazenes". Production is carried out, for example, via cyclophosphazene which is Petition 870240105284, dated 10 / 12 / 2024, pp. 68 / 95 56 / 77 obtained from PCI5 and NH4CI, in which the chlorine groups in cyclophosphazene were replaced by phenoxy groups by reaction with phenol.

[290] The cyclic phenoxyphosphazene compound can, for example, be produced as described in Allcock, HR, "Phosphorus-Nitrogen Compounds” (Academic Press, 1972), and in Mark, J.E., Allcock, H.R., West, R., “Inorganic Polymers” (Prentice Hall, 1992).

[291] Component E is preferably a mixture of cyclic phenoxyphosphazenes with three and four phenoxyphosphazene units. The weight ratio of rings comprising three phenoxyphosphazene units to rings comprising four phenoxyphosphazene units is preferably about 80:20. Larger rings of phenoxyphosphazene units may also be present, but in smaller amounts. Suitable cyclic phenoxyphosphazenes can be obtained from Fushimi Pharmaceutical Co., Ltd., under the name Rabitle®FP-100. This is a white-matte / yellowish solid with a melting point of 110 °C, a phosphorus content of 13.4% and a nitrogen content of 6.0%. The proportion of rings comprising three phenoxyphosphazene units is at least 80.0% by weight.

[292] Thermoplastic molding materials may preferably comprise 1.0 to 6.0% by weight, preferably 2.5 to 5.5% by weight, in particular 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.

[293] For this reason, especially solid non-migratory phosphate esters with a melting point between 70 °C and 150 °C are preferred. This makes the products easy to measure and exhibits noticeably less migration in the molding material. Particularly preferred examples are the commercially available PX-200® phosphate esters (CAS: 139189-30-3) from Daihachi, or Sol-DP® from ICL-IP. Other phosphate esters with appropriate substitution of the phenyl groups are conceivable when this allows the preferred melting range to be achieved. Petition 870240105284, dated 10 / 12 / 2024, p. 69 / 95 57 / 77 The general structural formula, depending on the substitution pattern in the ortho or para position on the aromatic ring, is as follows: (R6)m or (R4), (R2), (R3)m (R1) (R6)m (R5)m (R1)m or (R6)m Petition 870240105284, dated 10 / 12 / 2024, p. 70 / 95 58 / 77 where: R1 = H, methyl, ethyl or isopropyl, but preferably H. n = between 0 and 7, but preferably 0. R2-6 = H, methyl, ethyl or isopropyl, but preferably methyl. R6 is preferably identical to R4 and R5. m = can be, but not necessarily, identical and is between 1, 2, 3, 4 and 5, but preferably 2. R” = can be H, methyl, ethyl or cyclopropyl, but preferably methyl and H.

[294] The PX-200 is given as a concrete example:

[295] It is particularly preferable when using at least one aromatic ester of polyphosphoric acid. Such aromatic polyphosphates can be obtained, for example, from Daihachi Chemical under the name PX-200.

[296] As component E, the thermoplastic molding materials according to the invention may comprise 5.0 to 30.0% by weight, preferably 10.0 to 25.0% by weight, in particular 12.0 to 20.0% by weight, for example, about 16.0% by weight, of at least one metal phosphinate or salt of phosphinic acid described below as a flame retardant.

[297] Examples of preferred flame retardants of component E are metal phosphinates derived from hypophosphorous acid. A metal salt of hypophosphorous acid with Mg, Ca, Al or Zn as the metal can Petition 870240105284, dated 10 / 12 / 2024, p. 71 / 95 59 / 77, for example, can be used. Particular preference is given to aluminum hypophosphite.

[298] In addition, phosphinic acid salts of formula (I) and / or diphosphinic acid salts of formula (II) or their polymers are suitable. R1 Mm+ 2Mxm+ where R1 and R2 are identical or different and represent hydrogen, linear or branched C1-C6 alkyl, and / or aryl; R3 represents linear or branched C1-Cw-alkylene, C6-C10-arylene, -alkylarylene or -arylalkylene; 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; m = 1 to 4; n = 1 to 4; x = 1 to 4, preferably m = 3, x = 3.

[299] Preferably, R1, R2 are identical or different and represent hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl and / or phenyl.

[300] Preferably, R3 represents 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.

[301] In a particularly preferred manner, R1, R2 are hydrogen, methyl, ethyl, and M is Al, and particular preference is given to Al hypophosphite.

[302] The production of phosphinates is preferably carried out by Petition 870240105284, dated 10 / 12 / 2024, p. 72 / 95 60 / 77 precipitation of the corresponding metallic salts from aqueous solutions. However, phosphinates can also be precipitated in the presence of a suitable inorganic metal oxide or sulfide as a support material (white pigments, for example, TO2, SnO2, ZnO, ZnS, SO2). This provides modified surface pigments that can be used as laser-markable flame retardants for thermoplastic polyesters.

[303] It is preferable when metal salts of substituted phosphinic acids are employed in which, compared with hypophosphorous acid, one or two hydrogen atoms have been replaced by phenyl, methyl, ethyl, propyl, isobutyl, iso-octyl or R'-CH-OH radicals have been replaced by R'-hydrogen, phenyl, tolyl. The metal is preferably Mg, Ca, Al, Zn, Ti, Fe. Aluminum diethylphosphinate (DEPAL) is particularly preferred.

[304] For a description of phosphinic acid salts or diphosphinic acid salts, reference may be made to document DE-A 199 60 671 and also to documents DE-A 44 30 932 and DE-A 199 33 901.

[305] Other flame retardants are, for example, flame retardants containing halogen.

[306] Suitable halogen-containing flame retardants are preferably brominated compounds, such as brominated diphenyl ether, brominated trimethylphenylindane (DSB FR 1808), tetrabromobisphenol A and hexabromocyclododecane.

[307] Suitable flame retardants are preferably brominated compounds, such as brominated oligocarbonates (BC 52 or BC 58 from Great Lakes) with the structural formula: / Br Br \ --(O)--(O)— OCO-- '—\ / — II i \ Br Br O n < 3 Petition 870240105284, dated 10 / 12 / 2024, page 73 / 95 61 / 77

[308] Polypentabromobenzyl acrylates are particularly suitable, where n > 4 (for example, ICL-IP FR 1025 having the formula:

[309] Preferred brominated compounds also include products of the oligomeric reaction (n > 3) of tetrabromobisphenol A with epoxides (e.g., FR 2300 and 2400 from DSB) having the formula:

[310] Brominated oligostyrenes preferably used as flame retardants have an average degree of polymerization (number mean) between 3 and 90, preferably between 5 and 60, measured by vapor pressure osmometry in toluene. Cyclic oligomers are equally suitable. In a preferred embodiment of the invention, brominated oligomeric styrenes have the formula I shown below, wherein R represents hydrogen or an aliphatic radical, in particular an alkyl radical, for example, CH2 or C2H5, and en represents the number of repeating building blocks of the chain. R1 can be H or bromine or else a fragment of a usual free radical former: (I) Petition 870240105284, dated 10 / 12 / 2024, p. 74 / 95 62 / 77

[311] The value n can be 1 to 88, preferably 3 to 58. Brominated oligostyrenes comprise 40.0 to 80.0% by weight, preferably 55.0 to 70.0% by weight, of bromine. Preference is given to a product consisting predominantly of polydibromostyrene. The substances are fusible without decomposing and soluble in tetrahydrofuran, for example. The said substances can be produced by ring bromination of - optionally aliphatically hydrogenated - styrene oligomers, such as are obtained, for example, by thermal polymerization of styrene (according to DT-OS 25 37 385) or by free radical oligomerization of suitable brominated styrenes. The flame retardant can also be produced by ionic oligomerization of styrene and subsequent bromination. The amount of brominated oligostyrene needed to give polyamides flame-retardant properties depends on the bromine content.The bromine content in the molding materials according to the invention is from 2.0 to 30.0% by weight, preferably from 5.0 to 12.0% by weight.

[312] Brominated polystyrenes according to the invention are typically obtained by the process described in document EP-A 047 549: — (—CH-CH2-)-n — (—CH-CH2-)-n' I SbCl31 +3BrCl CH2--CH2' II Br3+ 3HCl ClCl (II)(III) .

[313] Brominated polystyrenes obtained by this process and commercially available are predominantly tribrominated products with a substituted ring. n' (see III) generally has values ​​from 125 to 1500, which corresponds to a molecular weight of 42,500 to 235,000, preferably from 130,000 to 135,000. Petition 870240105284, dated 10 / 12 / 2024, pp. 75 / 95 63 / 77

[314] The bromine content (based on the amount of bromine substituted in the ring) is generally at least 50.0% by weight, preferably at least 60.0% by weight and in particular 65.0% by weight.

[315] Commercially available powder products generally have a glass transition temperature of 160 °C to 200 °C and can be obtained, for example, under the names SAYTEX® HP-7010 from Albemarle and Pyrocheck® PB 68 from Ferro Corporation.

[316] Mixtures of brominated oligostyrenes with brominated polystyrenes can also be used in the molding materials according to the invention, the mixing ratio being freely selectable.

[317] Chlorine-containing flame retardants are also suitable, with Declorane Plus® from Oxychem being preferable.

[318] Suitable halogen-containing flame retardants are preferably brominated polystyrene, brominated polybenzyl acrylates, brominated bisphenol A epoxide oligomers or brominated bisphenol A polycarbonates.

[319] In one embodiment of the invention, halogen-containing flame retardants are not used in the thermoplastic molding materials according to the invention.

[320] A suitable flame-retardant melamine compound as component E in the context of the present invention is a melamine compound that, when added to glass fiber-filled polyamide molding materials, reduces flammability and influences fire behavior in a flame-retardant manner, thereby resulting in improved properties in the UL 94 Test and the glowing wire test.

[321] The melamine compound is, for example, selected from melamine borate, melamine phosphate, melamine sulfate, Petition 870240105284, dated 10 / 12 / 2024, pp. 76 / 95 64 / 77 melamine pyrophosphate, melam, melem, melon or melamine cyanurate or mixtures thereof.

[322] 0 melamine cyanurate preferably suitable according to the invention is a reaction product of preferably equimolar amounts of melamine (formula I) and cyanuric acid / isocyanuric acid (formulas Ia and Ib). NH2 N'C'N I II curc / NX h2n nh2 OH n'c'n I II / 'NX HO OH (Ia) forms enol (Ib) forms keto

[323] The same is obtained, for example, by reacting aqueous solutions of the starting compounds at 90 °C to 100 °C. The commercially available product is a white powder with an average grain size dso of 1.5 to 7 pm and a dgg value of less than 50 pm.

[324] Other suitable compounds (often also described as salts or adducts) are melamine sulfate, melamine, melamine borate, oxalate, prim. phosphate, see. phosphate and see. pyrophosphate, melamine borate neopentyl glycol. According to the invention, the molding materials are preferably free of polymeric melamine phosphate (CAS No. 56386-64-2 or 218768-84-4).

[325] This should be understood as meaning melamine polyphosphate salts of a 1,3,5-triazine compound having an average degree of condensation number n between 20 and 200 and a content of 1,3,5 Petition 870240105284, dated 10 / 12 / 2024, pp. 77 / 95 65 / 77 triazine from 1.1 to 2.0 mol of a 1,3,5-triazine compound selected from the group consisting of melamine, melam, melem, melon, amelina, amelida, 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% by weight aqueous salt paste produced according to EP-B1 095 030 will generally be greater 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 to a 300 mL beaker, stirring the resulting aqueous paste for 30 minutes, and then measuring the pH. The n value mentioned above, the numerical mean degree of condensation, can be determined by 31P NMR in the solid state. JR van Wazer, CF Callis, J. Shoolery and R. Jones, J. Am. Chem. Soc.Studies in 78, 5715, and 1956 reveal that the number of adjacent phosphate groups gives a unique chemical shift that allows a clear distinction between orthophosphates, pyrophosphates, and polyphosphates.

[326] Suitable guanidine salts are CAS No. 593-85-1, 593-85-1, 70285-19-7, 5423-22-3, 5423-23-4, 646-34-4, 594-14-9, pentaerythritol guanidine borate, neopentylglycol guanidine borate, and 4861-19-2 urea phosphate Petition 870240105284, dated 10 / 12 / 2024, pp. 78 / 95 66 / 77 urea cyanurate 57517-11-0 amelina 645-92-1 amelida 645-93-2 melem 1502-47-2 melon 32518-77-7

[327] In the context of the present invention, "compounds" should be understood to mean, for example, benzoguanamine itself and its adducts / salts, but also nitrogen-substituted derivatives and their adducts / salts.

[328] Also suitable are ammonium polyphosphate (NH4PO3)n where n is about 200 to 1000, preferably 600 to 800, and tris(hydroxyethyl)isocyanurate (THEIC) of formula IV O ü HOH4C-N N-C2H4OH IV O^N^O C2h4oh or the reaction products thereof with aromatic carboxylic acids Ar(COOH)m which may optionally be present in a mutual mixture, wherein Ar represents an aromatic ring system having six monocyclic, bicyclic or tricyclic members in e 2, 3 or 4.

[329] Examples of suitable carboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, 1,3,5-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, pyromellitic acid, melanophanic acid, prenitic acid, 1-naphthoic acid, 2-naphthoic acid, naphthalenedicarboxylic acids and anthracenecarboxylic acids.

[330] Production is carried out by reacting tris(hydroxyethyl)isocyanurate with acids, their alkyl esters or their halides according to the processes in EP-A 584 567. Petition 870240105284, dated 10 / 12 / 2024, pp. 79 / 95 67 / 77

[331] These reaction products are a mixture of monomeric and oligomeric esters which may also be crosslinked. The degree of oligomerization is typically from 2 to about 100, preferably from 2 to 20. Preference is given to the use of mixtures of THEIC and / or reaction products thereof with phosphorus-containing nitrogen compounds, in particular (NH4PO3)n or melamine pyrophosphate or polymeric melamine phosphate. The mixing ratio, for example, of (NH4PO3)n to THEIC is preferably 90.0 to 50.0:10.0 to 50.0, in particular 80.0 to 50.0:50.0 to 20.0% by weight based on the mixture of such compounds.

[332] Benzoguanidine compounds of formula V are also suitable flame retardants. NRR' N / ^ / n __ RR'N^N-< <o>(V), where R, R' represents linear or branched chain alkyl radicals with 1 to 10 carbon atoms, preferably hydrogen, and in particular adducts of these with phosphoric acid, boric acid and / or pyrophosphoric acid.

[333] Allantoin compounds of formula VI are also preferred, (VI) where R, R' are as defined in formula V, and also their salts with phosphoric acid, boric acid and / or pyrophosphoric acid and also glycoluryls of formula VII or their salts with the acids mentioned above RR N—|—NO=( )=° (VII) N—*—N ( ) RR Petition 870240105284, dated 10 / 12 / 2024, pp. 80 / 95 68 / 77 where R is as defined in formula V.

[334] Suitable products are commercially available or can be obtained in accordance with document DE-A 196 14 424.

[335] The usable cyanoguanidine (formula VIII) according to the invention can be obtained, for example, by the reaction of calcium cyanamide with carbonic acid, the cyanamide being produced by dimerization at pH 9 to pH 10 to provide cyanoguanidine. CaNCN + HO CO2----H HN-CN + CaCO3pH 9-10 H2N2 H2N - CN---------► ^C=N-CN HN V VIII h2nx / CN-CN HNX H.

[336] The commercially available product is a white powder with a melting point of 209 °C to 211 °C.

[337] It is particularly preferable to use melamine cyanurate (e.g., Melapur® MC25 from BASF SE).

[338] It is also possible to use separate metal oxides such as antimony trioxide, antimony pentoxide, sodium antimonate and similar metal oxides. However, it is preferable to avoid the use of such metal oxide, since they are already present in component F. For a description of pentabromobenzyl acrylate and antimony trioxide or antimony pentoxide, reference may be made to document EP-A 0 624 626.

[339] It is also possible to use phosphorus, for example, red phosphorus, as a flame retardant. Red phosphorus can, for example, be used in the form of a masterbatch.

[340] Dicarboxylic acids with the formula are also contemplated. Petition 870240105284, dated 10 / 12 / 2024, pp. 81 / 95 69 / 77 Mx where: R1a R4, independently of each other, represents halogen or hydrogen with the condition that at least one radical R1a R4 represents halogen, x = 1 to 3, preferably 1, 2 m = 1 to 9, preferably 1 to 3, 6, 9, in particular 1 to 3 n = 2 to 3 M = alkaline earth metal, Ni, Ce, Fe, In, Ga, Al, Pb, Y, Zn, Hg.

[341] Preferred dicarboxylic acid salts comprise, independently of each other, Cl or bromine or hydrogen as radicals R1a R4, especially preferably all radicals R1a R4 are Cl and / or Br.

[342] Be, Mg, Ca, Sr, Ba, Al, Zn, Fe are preferred as M metals.

[343] Such dicarboxylic acid salts are commercially available or can be produced according to the processes described in US Patent 3,354,191.

[344] Functional polymers are also usable as component E. These can be flame-retardant polymers, for example. Such polymers are described in US Patent 8,314,202, for example, Petition 870240105284, dated 10 / 12 / 2024, pp. 82 / 95 70 / 77 and comprise repeating units of 1,2-bis[4-(2-hydroxyethoxy)phenyl]ethanone. An additional functional polymer suitable for increasing the amount of carbon residue is poly(2,6-dimethyl-1,4-phenyleneoxide) (PPPO).

[345] The thermoplastic molding compositions of the invention can be produced by processes known per se, mixing the starting components in conventional mixing apparatus, such as screw-based extruders, Brabender mixers or Banbury mixers, and then extruding them. After extrusion, the extrudate can be cooled and pelletized. It is also possible to premix individual components and then add the remaining starting materials individually and / or equally in the form of a mixture. Mixing temperatures are generally from 200 to 320 °C.

[346] These materials are suitable for the production of fibers, sheets and molds of any kind. Here are some examples: extruded tubes, for example, for automotive applications (e.g. brake fluid tubes), cable routing systems or cable management systems (clamps, corrugated tubes), shoe soles, dies for the production of rubber tubes (mandrels), sporting equipment such as ski boots or football shoes.

[347] The invention is further illustrated by the following examples. Examples Example I Preparation of Plasticized Polyolefin / PA 6 Blends and Testing in Pipe Extrusion

[348] The polymers shown in Table 1 below were compounded with the other components, as indicated in Table 1, in a ZE40 twin-screw extruder at 95 kg / h through a round nozzle with Petition 870240105284, dated 10 / 12 / 2024, pp. 83 / 95 71 / 77 with a diameter of 3 mm. Liquid plasticizers were dosed directly into the molten polymer. Granules of the polymer composition were obtained. These granules were processed by standard injection molding to obtain tensile bars or plates. In addition, bars with a diameter of 14.5 cm were extruded from the granules. They were tested for extrusion applications. Injection molding was performed at a melting temperature of 250°C. The results are listed in Table 1 below.

[349] The quantities listed in the following tables are % by weight.

[350] The following components were used: PA 1: Polyamide-6 having a relative viscosity of 2.4 (measured according to ISO 307, 1157, 1628 (0.5% in 96% H2SO4) (Ultramid® B24 N 03 from BASF SE) PA 2: Polyamide-6 with approximately 10% by weight of caprolactam (Ultramid® B25 M 01 from BASF SE) PA 3: Polyamide-6 / 6,36 (hydrogenated), with a relative viscosity of 2.7 (measured according to ISO 307, 1157, 1628 (0.5% in phenol / orthodichlorobenzene 50:50) (Ultramid® RX2298 from BASF SE) PA 4: Polyamide-6 / 6,36 having a relative viscosity of 2.9 (measured according to ISO 307, 1157, 1628 (0.5% in phenol / orthodichlorobenzene 50:50)) (Ultramid® F29 from BASF SE) Plasticizer 1: N-(2-hydroxypropyl)benzene sulfonamide (Proviplast®2102 from Proviron) Plasticizer 2: Tetraethylene glycol (from Sigma-Aldrich) Plasticizer 3: Lauryl-lactam (from Sigma-Aldrich) Plasticizer 4: Caprolactam Tablets Plasticizer 5: Polyethylene glycol 400 (PEG400) (from SigmaAldrich) Plasticizer 6: Polyethylene glycol 6000 (PEG6000) (from Sigma Petition 870240105284, dated 10 / 12 / 2024, p. 84 / 95) 72 / 77 Aldrich) Elastomer 1: Ethylene-propylene rubber grafted with maleic anhydride (Exxelor® VA1801 from ExxonMobil Chemical) Elastomer 2: Ethylene-butyl acrylate copolymer (LUCALEN® A2540D from Basell) Stabilizer 1: Irganox® B1171 from BASF SE Stabilizer 2: Irganox® 1076 from BASF SE Stabilizer 3: Irganox® 1098 from BASF SE Stabilizer 4: Sodium hypophosphite monohydrate Stabilizer 5: Irgafos® 126 from BASF SE Glass fiber: PA-PBG-3660 Lubricant 1: Ethylene-bis-stearamide (EBS), Acrawachs® C from Lonza Cologne GmbH Lubricant 2: Calcium stearate (Ceasit AV from Baerlocher) GmbH) Dye: Master batch of carbon black (Ultrabatch 420 from BASF SE) Table 1 COMP1a COMP1b 1 COMP1c 2 COMP 1d PA 1 57 54.5 54.5 52 52 PA 2 57 Elastomer 1 15 15 15 15 15 15 Stabilizer 1 0.5 0.5 0.5 0.5 0.5 0.5 Stabilizer 2 0.1 0.1 0.1 0.1 0.1 0.1 TALKUM100 / IT Extra 0.4 0.4 0.4 0.4 0.4 0.4 Elastomer 2 25 25 25 25 25 25 PA 3 2.0 2.0 2.0 2.0 2.0 2.0 Plasticizer 1 2.5 5 Plasticizer 2 2.5 5 Processing: Tube extrusion (Pilot center, LU F206) ++ OK, smoke at the nozzle ++ OK, smoke at the nozzle ++ Smoke and deposit at the nozzle MVR 275 / 5kg, ISO1133 9 23 11 10 13 6 Modulus of elasticity (dry / condensed), ISO 527 1000 / 347 938 / 216 588 / 260 588 / 216 376 / 239 680 / 285 Petition 870240105284, dated 10 / 12 / 2024, pp. 85 / 95 73 / 77 COMP1a COMP1b 1 COMP1c 2 COMP 1d Tensile strength at break (dry / cond.), ISO527 35 / 30 36 / 19 37 / 34 36 / 17 35 / 34 35 / 37 Elongation at break (dry / cond.), ISO527 200 / 316 203 / 318 264 / 340 256 / 330 261 / 320 189 / 320 Charpy impact with notch (23 °C) (dry / cond.), ISO 179 / 1eA 99 / NB 101 / NB 104 / NB 100 / NB NB / NB 102 / NB Charpy impact with notch (-30 °C) (dry) ISO 179 / 1eA 23 20 24 20 21 19 Glass transition temperature (DMTA) 55 45 35 35 13 -

[351] The ISO standards are those valid in 2020.

[352] From the results it is evident that tetraethylene glycol (plasticizer 2) shows a significantly greater decrease in the modulus of elasticity when compared to sulfonamide of plasticizer 1 at the same application levels. Example II Preparation of Reinforced Plasticized Fiberglass and PA 6 and Impact Modified

[353] The compositions defined in Table 2 below (quantities in % by weight) were compounded in a ZE25 twin-screw extruder at 45 kg / h and extruded through a round nozzle with a diameter of 3 mm. The plasticizer and lubricant were added directly to the melt.

[354] The granules were injection molded and the molds were characterized as indicated in Table 2. Table 2 COMP 2a 3 4 PA 1 51.2 49.2 46.2 Plasticizer 2 0 2 5 Elastomer 1 5 5 5 Elastomer 2 10 10 10 Fiberglass 30 30 30 Lubricant 1 0.2 0.2 0.2 Lubricant 2 0.1 0.1 0.1 Stabilizer 3 0.15 0.15 0.15 Dye 3.35 3.35 3.35 Petition 870240105284, dated 10 / 12 / 2024, pp. 86 / 95 74 / 77 COMP 2a 3 4 MVR 275 / 5kg, ISO1133 54 77 134 Modulus of elasticity (dry / cond.), ISO 527 7663 / 4450 6824 / 4228 5593 / 4215 Tensile strength at break (dry / cond.), ISO527 115 / 80 107 / 78 94 / 77 Elongation at break (dry / cond.), ISO527 4.5 / 11.6 6.0 / 10.5 8.4 / 8.4 Charpy impact with notch (23 °C) (dry / cond.) ISO 179 / 1eA 15 / 21 14 / 24 16 / 25 Charpy impact with notch (-30 °C) (dry), ISO 179 / 1eA 10 9 8

[355] By including tetraethylene glycol (plasticizer 2), the tensile strength at break (dry) can be significantly improved. Example III Preparation of PA 6 / 6.36 Based Plasticized Compounds

[356] The components listed in Table 3 below (in % by weight) were compounded in a ZSK25 twin-screw extruder at 16 kg / h, followed by submerged granulation. Plasticizers were added directly to the melt.

[357] The granules obtained were injection molded and the molds were characterized. The results are summarized in Table 3 below. Table 3 5 6 COMP 3a COMP 3b COMP 3c COMP 3d COMP 3e COMP 3f PA 4 96.34 95.34 92.84 87.84 92.84 87.84 92.84 87.84 Lubricant 2 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Lubricant 1 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 TALKUM 100 / Talkum IT extra 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 Stabilizer 4 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Stabilizer 5 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 Stabilizer 3 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 Plasticizer 2 2.5 3.5 Plasticizer 1 5 10 Plasticizer 3 5 10 Plasticizer 4 5 10 Evaluation of injection molded parts, ISO1133 ++ ++ OK OK White efflorescence after several days White efflorescence after several days Bad smell Bad smell Petition 870240105284, dated 10 / 12 / 2024, pp. 87 / 95 75 / 77 5 6 COMP 3a COMP 3b COMP 3c COMP 3d COMP 3e COMP 3f Modulus of elasticity (dry / condensed), ISO 527 788 / 464 680 / 457 657 / 403 433 / 342 945 / 431 599 / 381 533 / 386 347 / 342 Tensile strength at break (dry / condensed), ISO527 32 / 26 30 / 26 29 / 24 23 / 20 34 / 25 25 / 23 27 / 23 20 / 20 Elongation at break (dry / condensed), ISO527 436 / 402 415 / 390 337 / 390 398 / 375 358 / 354 429 / 416 424 / 390 373 / 378 Charpy impact with notch (23 °C) (dry / cond.) ISO 179 / 1eA 11 / nb 16 / nb 9 / nb 24 / nb 5 / nb 5 / nb 19 / nbnb / nb Charpy impact with notch (-30 °C) (dry), ISO 179 / 1eA 5 4 4 3 5 3 3 3 MVR 275 / 5 kg, ISO1133 190 220 287 >300 193 262 185 184

[358] Some of the comparative moldings showed white efflorescence after several days or had an inappropriate bad smell, so the moldings were not of practical use.

[359] The modulus of elasticity, tensile strength at yield, and tensile strength improve for molds made from compositions 5 and 6. Example IV

[360] In Example 4, modified impact formulations comparable to Example 1 with 2.5 and 4.0 wt% tetraethylene glycol (Examples 7 and 8) were compared with formulations containing polyethylene glycol 400 (PEG400) (Examples compounds 1e and 1f) and polyethylene glycol 6000 (PEG6000) (Examples compounds 1g and 1h) with a similar loading. The modulus of elasticity in the dry state shows the plasticizing effect (low Petition 870240105284, dated 10 / 12 / 2024, pages 88 / 95 76 / 77 modulus of elasticity -> high plasticizing effect).

[361] The inventive materials that are plasticized with tetraethylene glycol exhibit a lower modulus of elasticity. In the case of tetraethylene glycol, increasing the plasticizer content from 2.5% by weight to 4% by weight results in a very soft material with a modulus of elasticity of 428 MPa. In the case of PEG400 and PEG6000, increasing the plasticizer content from 2.5% to 4.0% by weight no longer has such a significant plasticizing effect. Most likely, the solubility of PEG400 and PEG6000 in polyamide is limited, so that only a small plasticizing effect at low loads below 4% by weight can be obtained with these plasticizers.

[362] The polymers shown in Table 4 below were compounded with the other components, as indicated in Table 4, in a ZSK25 twin-screw extruder at 15 kg / h through a round nozzle having a diameter of 2 mm and a submerged granulation. Liquid plasticizers were dosed directly into the molten polymer. Granules of the polymeric composition were obtained. These granules were processed by standard injection molding to obtain tensile bars or plates. Injection molding was carried out at a melting temperature of 250°C. The results are listed in the following Table. 7* 8 COMP1e COMP1f COMP1g COMP1h PA 1 54.5 53 54.5 53 54.5 53 PA 2 Elastomer 1 15 15 15 15 15 15 Stabilizer 1 0.5 0.5 0.5 0.5 0.5 0.5 Stabilizer 2 0.1 0.1 0.1 0.1 0.1 0.1 TALKUM100 / IT Extra 0.4 0.4 0.4 0.4 0.4 0.4 Elastomer 2 25 25 25 25 25 25 PA 3 2.0 2.0 2.0 2.0 2.0 2.0 Plasticizer 2 2.5 4 Plasticizer 5 2.5 4 Plasticizer 6 2.5 4 MVR 275 / 5kg, ISO1133 36 44 38 49 23 23 Modulus of elasticity 623 / - 428 / - 741 / - 659 / - 972 / - 920 / - Petition 870240105284, dated 10 / 12 / 2024, pp. 89 / 95 77 / 77 7* 8 COMP1e COMP1f COMP1g COMP1h (dry / conditioned), ISO 527 Tensile strength at break (dry / conditioned), ISO527 28 / - 28 / - 31 / - 29 / - 30 / - 29 / - Elongation at break (dry / conditioned), ISO527 175 / - 215 / - 193 / - 194 / - 157 / - 158 / - Charpy impact with notch (23 °C) (dry / conditioned), ISO 179 / 1eA 92 / - 90 / - 97 / - 86 / - 90 / - 90 / - Charpy impact with notch (-30 °C) (dry) ISO 179 / 1eA 19 17 20 17 22 27 Formulation Example 7 is comparable to Example 1, but the composition was carried out in a different extruder.< / o> < / c> < / c>

Claims

1. THERMOPLASTIC MOLDING COMPOSITION, characterized by comprising: (a) 39.9 to 99.9% by weight of at least one thermoplastic polyamide as component A, (b) 0.1 to 10% by weight of at least one plasticizer of the general formula (1) R1-O-(CH2CH2-O-)nR2 (1) with n = 1 to 4 Ri, R2 being independently H, C1-12 alkyl, phenyl or tolyl, with a boiling point above 250 °C, as component B, (c) 0 to 45% by weight of at least one elastomeric polymer as component C, (d) 0 to 60% by weight of at least one fibrous and / or particulate filler, as component D, (e) 0 to 25% by weight of additional additives, as component E, wherein the total % by weight of components A to E It is 100% by weight.

2. COMPOSITION, according to claim 1, characterized in that component B has a boiling point of at least 290 °C, preferably at least 300 °C.

3. COMPOSITION, according to any one of claims 1 to 2, characterized in that, in the general formula (1), R1 and R2 are independently H or C1-8 alkyl, preferably H or C1-3 alkyl, more preferably H.

4. COMPOSITION, according to any of the claims 1 to 3, characterized by component A being an aliphatic polyamide or a semi-aromatic polyamide.

5. COMPOSITION, according to any one of claims 1 to 4, characterized in that component A is selected from PA 6, PA 66, PA 6 / 66, PA 66 / 6, PA 12, PA 6.10, PA 6T / 6, PA 6I / 6T, PA 6T / 6I, PA 9T, PA 4T and copolyamides produced by polymerization of the components: (A') 15% to 84% by weight of at least one lactam, (B') 16% to 85% by weight of a mixture of monomers (M) comprising the components, (B1') at least one C32-C40 dimeric acid, and (B2') at least one C4-C12 diamine, wherein the percentages by weight of components (A') and (B') are, in each case, based on the sum of the percentages by weight of components (A') and (B'). (B'), or mixtures thereof, and is preferably selected from PA 6, PA 66, PA 6 / 66, PA 66 / 6, PA 6 / 6.36 or mixtures thereof.

6. COMPOSITION, according to any one of claims 1 to 5, characterized in that component C is present in an amount of 1 to 45% by weight and is selected from: (b1) ethylene copolymers with at least one comonomer selected from C3-12 olefins, C1-12 alkyl (meth)acrylates, (meth)acrylic acid and maleic anhydride as component (B1); (b2) polyethylene or polypropylene as component (B2), wherein components (B1) and (B2) may also be additionally grafted with maleic anhydride and are preferably selected from ethylene-propylene rubbers, ethylene-propylene-diene rubbers, ethylene-butylacrylate copolymers, ethylene and / or propylene copolymers and maleic anhydride. Petition 870240105284, dated 10 / 12 / 2024, pp. 92 / 95 3 / 4 7. COMPOSITION, according to any one of claims 1 to 6, characterized in that component D comprises glass fibers and is present in an amount of 10 to 50% by weight, preferably 15 to 45% by weight, more preferably 20 to 40% by weight.

8. PROCESS FOR PREPARING THE THERMOPLASTIC MOLDING COMPOSITION, as defined in any one of claims 1 to 7, characterized by comprising mixing components A to E.

9. USE OF THE THERMOPLASTIC MOLDING COMPOSITION, as defined in any one of claims 1 to 7, characterized by being for the production of fibers, sheets and molds of any type.

10. FIBER, SHEET OR MOLD, characterized by being produced by thermoplastic molding composition, as defined in any one of claims 1 to 7.

11. USE OF A COMPOUND, of general formula (1) R1-O-(CH2CH2-O-)nR2 (1) with n = 1 to 4 Ri, R2 being independently H, C1-12 alkyl, phenyl or tolyl, with a boiling point above 250 °C, characterized by being a plasticizer for thermoplastic polyamides.

12. USE, according to claim 11, characterized in that the compound of general formula (1) has a boiling point of at least 290 °C, preferably at least 300 °C.

13. USE, according to any one of claims 11 to 12, characterized in that, in general formula (1), R1 and R2 are independently H Petition 870240105284, dated 10 / 12 / 2024, p. 93 / 95 4 / 4 or C1-8 alkyl, preferably H or C1-3 alkyl, more preferably H.