Recycling method for producing polyamide compounds

Abstract

A process for producing polyamide B, comprising melt-mixing polyamide A and a salt C of a diacid and a diamine, wherein the polyamide B has a lower viscosity number than the polyamide A and has a specific ratio of the ratio of the concentration of amino end groups of polyamide B to the concentration of amino end groups of polyamide A to the ratio of the concentration of carboxyl end groups of polyamide B to the concentration of carboxyl end groups of polyamide A; polyamide B obtained by the above process; polyamide B * and a polyamide B1 composed of units derived from the diacid and diamine forming the salt C; a polyamide composition comprising the polyamide B or the polyamide B1, a filler material (D) and optionally at least one further additive (E); a polymer product comprising the polyamide B, the polyamide B1 or the polyamide composition; the use of the polyamide B, the polyamide B1 or the polyamide composition for producing a polymer product, and a method for producing a polymer product comprising the polyamide B, the polyamide B1 or the polyamide composition.

Description

Technical Field

[0001] The present invention relates to a method for producing polyamide B, which comprises melt-mixing polyamide A and a salt C of a diacid and a diamine, wherein polyamide B has a lower viscosity number than polyamide A, and the ratio of the concentration of amino end groups of polyamide B to the concentration of amino end groups of polyamide A, to the ratio of the concentration of carboxyl end groups of polyamide B to the concentration of carboxyl end groups of polyamide A, has a specific ratio; polyamide B obtained by the above method; polyamide B * and polyamide B1 composed of units derived from the diacid and diamine forming salt C; a polyamide composition comprising the polyamide B or the polyamide B1, a filler material (D) and optionally at least one further additive (E); a polymer product comprising the polyamide B, the polyamide B1 or the polyamide composition; the use of the polyamide B, the polyamide B1 or the polyamide composition for producing a polymer product, and a method for producing a polymer product comprising the polyamide B, the polyamide B1 or the polyamide composition.

Background Art

[0002] Polyamides (nylons) are regarded as high-performance plastics because they exhibit high temperature resistance and electrical resistance, and are widely used especially in the automotive and transportation markets, consumer goods, electrical and electronic applications, and in the manufacture of fibers. In the process of environmental protection, the recycling of polyamide waste materials is becoming increasingly important. Polyamides are suitable compounds for chemical recycling. Chemical recycling via the depolymerization of polyamides is a promising approach for reducing fossil raw materials in monomer synthesis and for reducing the amount of plastic waste.

[0003] Examples of known recycling methods via depolymerization are described below: U.S. Patent No. 3,069,465 (US 3069465) relates to a method for recovering adipic acid and hexamethylenediamine from polyhexamethylene adipamide (PA66) by continuously hydrolyzing the adipamide in an aqueous sulfuric acid solution.

[0004] U. Cesarek et al., ACS Sustainable Chem. Eng., 2020, 8, 16274 - 16282, relates to chemical recycling methods of aliphatic polyamides (PA) (PA66, PA1010, PA11, and PA12), wherein, even in the presence of reinforcing additives such as carbon fibers and glass fibers, PA is converted only to their constituent monomers. The hydrolysis reaction of PA is carried out under microwave irradiation in the presence of HCl as an acid catalyst.

[0005] U.S. Patent No. 5,310,905 (US 5310905) is a method for recovering caprolactam from waste polycaprolactam, which comprises feeding an acid of the formula

Chemical formula

[0006] In the above - mentioned recycling methods, the monomers of each polyamide are recovered. Then, the monomers can be polymerized again, optionally in the presence of fresh (i.e., non - recycled) monomers, to obtain polyamides.

[0007] In the above method, the molecular weight of the polyamide is reduced by the addition of an acid. However, the reduction of the molecular weight by the acid is difficult to control due to the high reaction rate in the melt, leading to a significant deterioration of the mechanical properties. Furthermore, the control of such a reaction becomes more difficult when polyamide starting materials with unspecified compositions and / or initial viscosities are used, such as mixed production waste and / or recycled materials. Therefore, such materials are not used for manufacturing high-quality products because large-scale preliminary investigations and trials are required to adjust the target viscosity.

[0008] However, from an environmental perspective, the recycling of polyamides by controlled partial depolymerization is advantageous, especially when lower grades of polyamides are required.

[0009] Regarding viscosity adjustment / control, there are methods known in the art. However, the said methods are not polyamide recycling methods but merely adjustment / control methods.

[0010] European Patent Application Publication No. 3553113 (EP 3553113A1) relates to a method for controlling the molecular structure and selective functionalization of polyamides, which includes the reaction of a polyamide with at least two of the following additives: a) a first additive containing an acid and / or acid anhydride and preferably a polymer carrier, b) a second additive containing an oxazoline and / or an amine optionally mixed with a carrier, c) a third additive containing a compound for chain extension or chain branching optionally mixed with a carrier, and the reaction of the polyamide with the at least two additives is carried out such that the reaction with one additive is first performed, followed by the reaction with a further additive.

[0011] International Publication No. 2018 / 072875 (WO 2018 / 072875) relates to an additive for controlling the viscosity of a polycondensate, the additive comprising an acid and / or an acid anhydride and a carrier, preferably a polymeric carrier, wherein the acid and / or the acid anhydride is homogeneously distributed in the carrier, a method for producing the additive, a method for controlling the viscosity of a polycondensate, and the use of the additive for controlling the controlled viscosity adjustment of a polycondensate.

[0012] A method for recycling by partial decomposition of polyamides is disclosed in German Patent Application Publication No. 4421239 (DE 4421239 A1). German Patent Application Publication No. 4421239 relates to a method for recycling high molecular weight nylon 6 (polyamide 6), a repolymer produced by this method, and a method for recycling used plastic parts made of high molecular weight nylon 6 or nylon 6, which uses a normal depolymerization step in the presence of caprolactam, water and an acid to provide a melt of a defined viscosity level, from which, after removal of components insoluble in the low viscosity melt, the remaining material is repolymerized or decomposed to provide a repolymer that can be further processed or to provide caprolactam, said method.

[0013] In B. Formisano et al., “Recycling of cast polyamide waste with a twin-screw-extruder”, uploaded on July 2, 2015 by Christian Bonten, at the 24. Stuttgarter Kunststoffkolloquium, cast polyamide 6 (PA6G) waste, which is not specified, is processed into an extrudable polyamide by compounding with a suitable additive. Rheological analysis and mechanical analysis have revealed both that the use of a lubricant is particularly advantageous and that the oxidized form provides a material with a low viscosity that can be injection molded.

[0014] French Patent Application Publication No. 3107059 (FR 3 107 059 A1) relates to a method for processing a polyamide composition intended for recycling, comprising: (i) supplying a mixture comprising a polyamide intended for recycling, a polyamide chain breaker, and optionally one or more fillers and / or additives; (ii) kneading the mixture in a molten state to obtain a composition having a target intrinsic viscosity; and (iii) recovering the composition obtained in step (ii). Suitable chain breakers are selected from water, carboxylic acids, amino acids, and / or mixtures thereof.

[0015] International Publication No. 2020 / 041259 (WO 2020 / 041259 A1) relates to a method for reducing the relative viscosity (RV) of a polyamide melt, comprising treating a first polyamide having an RV of 45 or more with an additive mixture comprising an organic dicarboxylic acid having a specific particle size distribution and a second polyamide having a specific particle size distribution, and melting the first polyamide treated with the additive mixture.

[0016] However, the subject matter of claims 11 and 12 of the article, and claims 13 to 18 that are dependent on or refer to claims 11 and 12 of the article, are not considered novel compared to U.S. Patent No. 6,187,877 (US 6,187,877 B1) (Citation 1), International Publication No. 2011 / 138397 (WO 2011 / 138397 A1) (Citation 2), Japanese Unexamined Patent Application Publication No. 2001-200054 (JP 2001 200054 A) (Citation 3), Japanese Unexamined Patent Application Publication No. 09-234789 (JP H09 234789 A) (Citation 4), International Publication No. 2018 / 165641 (WO 2018 / 165641) (Citation 5).

[0017] U.S. Patent No. 6,187,877 relates to a method for producing a polymer based on a dicarboxylic acid and a diamine by polycondensation in an extruder.

[0018] International Publication No. WO 2011 / 138397 relates to a method for producing polyamides containing monomer units of 1,4-diaminobutane and aliphatic linear carboxylic acids, PA-410 obtained by this method, and products manufactured therefrom.

[0019] Japanese Patent Application Laid-Open No. 2001-200054 relates to a method for producing nylon 6 copolymers and fibers having good dyeability with basic dyes. It is described that the nylon 6 copolymers are produced by the reaction of an aqueous ε-caprolactam solution containing salts of dicarboxylic acids and diamines and / or aminocarboxylic acids.

[0020] Japanese Patent Application Laid-Open No. 09-234789 relates to a method for producing an axially stretched film of polyamide. The polyamide is a terpolymer based on ε-caprolactam (85 to 99% by mass), aminododecanoic acid (0.5 to 5% by mass), and an equimolar salt of hexamethylenediamine and adipic acid (0.5 to 10% by mass).

[0021] International Publication No. WO 2018 / 165641 relates to a polyamide composition for use in forming wire or cable jacket compositions. The polyamide composition includes components of a polyamide 6 / 66 copolymer formed from substantially randomly distributed caprolactam monomers and hexamethylenediamine monomers.

Prior Art Documents

Patent Documents

[0022]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

[0023] [Non - Patent Document 1] U.Cesarek et al., ACS Sustainable Chem.Eng., 2020, 8, 16274 - 16282 [Non - Patent Document 2] B.Formisano et al., "Recycling of cast polyamide waste with a twin - screw - extruder", 24.Stuttgarter Kunststoffkolloquium [Summary of the Invention] [Problems to be Solved by the Invention]

[0024] The object of the present invention is a method for recycling polyamide, in particular post-industrial and / or post-consumer polyamide waste resulting from the extrusion industry, by reducing the molecular weight of the polyamide, which enables the production of recycled polyamide having good fluidity and sufficient melt stability, in particular for injection molding applications, and does not require complete depolymerization (recovery of monomers) followed by repolymerization of the recovered monomers.

[0025] In particular, in order to obtain an injection-moldable polyamide compound, a method that enables a defined and homogeneous reduction in viscosity and avoids further degradation of the produced compound is desirable.

Means for Solving the Problems

[0026] The above problem is solved by a method for producing polyamide B, which includes melt-mixing polyamide A and salt C of a diacid and a diamine, wherein polyamide B has a lower viscosity number than polyamide A, and the ratio (c NH2B / c NH2A ) of the concentration of amino end groups of polyamide B to the concentration of amino end groups of polyamide A, to the ratio (c COOHB / c COOHA ) of the concentration of carboxyl end groups of polyamide B to the concentration of carboxyl end groups of polyamide A, the ratio ((c NH2B / c NH2A ) / (c COOHB / c COOHA )) is 0.8 to 1.2 in polyamide B.

[0027] Preferably, (c NH2B / c NH2A ) / (c COOHB / c COOHA ) is 0.9 to 1.1.

[0028] The viscosity number (VN) of the polyamide and polyamide composition according to the present invention is measured in sulfuric acid in accordance with EN ISO 307:2019 (in 96 mass% [m / m] sulfuric acid at 25 °C, 0.5% [m / v] polyamide).

[0029] The melt volume flow rate (MVR) of the polyamide according to the present invention is measured in accordance with Procedure A of EN ISO 1133-1:2011.

[0030] The concentration of amino end groups (AEG [meq / kg]) of the polyamide disclosed in the present invention is measured by potentiometric titration of a polyamide-methanol-phenol solution with an aqueous hydrochloric acid solution. The concentration of carboxyl end groups (CEG [meq / kg]) of the polyamide disclosed in the present invention is measured by titrating a polyamide-benzyl alcohol solution with an alcoholic potassium hydroxide solution.

[0031] The above problems are further a) a polyamide B formed from units selected from combinations of one or more diamines and one or more diacids, one or more lactams, and mixtures thereof, in an amount of 99.00 to 99.99% by mass, preferably 99.10 to 99.90% by mass * and b) units derived from a diacid and a diamine forming a salt C, in an amount of 0.01 to 1% by mass, preferably 0.1 to 0.9% by mass The polyamide B1 composed of the above is such that the units derived from the diacid and the diamine forming the salt C are different from the units forming the polyamide B * This is solved by the above polyamide B1.

[0032] The above-mentioned problem is further solved by polyamide B obtained by the method according to the present invention, wherein the ratio of the amino end groups of polyamide B, measured by potentiometric titration of a polyamide-methanol-phenol solution with an aqueous hydrochloric acid solution, to the carboxylic acid end groups of polyamide B, measured by titration of a polyamide benzyl alcohol solution with an alcoholic potassium hydroxide solution, is preferably 0.2 or more, more preferably 0.40 or more, and most preferably 0.70 or more.

[0033] The above-mentioned problem is further (i) polyamide B or polyamide B1 according to the present invention, and (ii) optionally a filler material (D), and (iii) optionally at least one further additive (E) The problem is solved by a polyamide composition comprising the above, wherein at least one of one filler material (D) or one further additive (E) is present.

[0034] The above-mentioned problem is further solved by a polymer product comprising polyamide B, polyamide B1 or a polyamide composition according to the present invention, preferably an injection-molded part, by the use of polyamide B, polyamide B1 or a polyamide composition according to the present invention for manufacturing a polymer product, particularly an injection-molded part, and by a method for manufacturing a polymer product comprising converting polyamide B, polyamide B1 or a polyamide composition according to the present invention, preferably a manufacturing method comprising injection-molding polyamide B, polyamide B1 or a polyamide composition according to the present invention.

[0035] The present invention enables the ratio of the concentrations of the end groups (amino groups and carboxylic acid groups) of the starting polyamide to be maintained (with a deviation of about ±20%, preferably about ±10%). As a result, the melt stability of the recycled polyamide is ensured (MVR over time), that is, the MVR does not increase over time, or increases by less than 5% over time, preferably less than 3.5%, and more preferably the MVR does not increase over time, which is a prerequisite for applying recycled polymers, especially in injection molding, preferably at low additive concentrations.

[0036] Generally, polyamide B and further polyamide A can have any ratio of the concentration of amino end groups to the concentration of carboxyl end groups. Suitable ratios are 0.2 or more, preferably 0.40 or more, and more preferably 0.70 or more.

[0037] In the process of the present invention, only a small amount of the salt of the diacid and the diamine is required. The "salt of the diacid and the diamine" described in the present invention can be a salt of a single diacid and a single diamine. However, it is also possible for a mixture of two or more diacids and / or a mixture of two or more diamines to be present in the melt mixture.

[0038] Salt of diacid and diamine Preferably, the salt of the diacid and the diamine is present in an amount of 0.01 to 1% by weight, more preferably 0.1 to 0.9% by weight, and most preferably 0.15 to 0.5% by weight based on polyamide A. The diamine and the diacid are preferably in stoichiometric amounts and generally deviate from stoichiometry by 5 to 10%. If the (one or more) diacid and the (one or more) diamine are not used in the stoichiometric amounts required to form the salt, the amounts stated relate to the salt formed by the (one or more) diacid and the (one or more) diamine, and in addition to the amount of the salt stated, there may be an excess of free diacid or diamine.

[0039] The diacid is a dicarboxylic acid. In a preferred embodiment, the diacid is selected from the group consisting of adipic acid, glutaric acid, suberic acid, sebacic acid, dodecanedioic acid, 1,2- or 1,3-cyclohexanedicarboxylic acid, 1,2- or 1,3-phenylenediacetic acid, 1,2- or 1,3-cyclohexanediacetic acid, isophthalic acid, p-(tert-butyl)isophthalic acid, terephthalic acid, azelaic acid, pimelic acid, 4,4'-benzophenonedicarboxylic acid, 2,5-naphthalenedicarboxylic acid or 5-sulfoisophthalic acid or their alkali salts, and / or mixtures thereof. The preferred diacid is adipic acid.

[0040] In a preferred embodiment, the diamine is hexamethylenediamine, heptamethylenediamine, tetramethylenediamine, pentamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, 2-methylpentamethylenediamine, undecamethylenediamine, dodecamethylenediamine, xylylenediamine or isophoronediamine, 2-methylhexamethylenediamine, 3-methylhexamethylenediamine, 2,5-dimethylhexamethylenediamine, 2,2-dimethylpentamethylenediamine, 5-methylnonanediamine, 2,2,4- and 2,4,4-trimethylhexamethylenediamine, 2,2,7,7-tetramethyloctamethylenediamine, meta-xylylenediamine, para-xylylenediamine, diaminodicyclohexylmethane, and C2-C 16 -aliphatic diamines and / or mixtures thereof. The preferred diamine is hexamethylenediamine.

[0041] More preferably, the salt of the diacid and the diamine is the hexamethylenediamine adipate salt.

[0042] Polyamides A and B The viscosity numbers of polyamides A and B are generally not critical as long as polyamide B has a lower viscosity number than polyamide A.

[0043] The viscosity number of polyamide A is preferably 120 to 250 cm 3 / g, more preferably 150 to 220 cm 3 / g, and most preferably 170 to 210 cm 3 / g.

[0044] The viscosity number of polyamide B, as well as that of polyamide B1, is preferably 80 to 200 cm 3 / g, more preferably 100 to 180 cm 3 / g, and most preferably 120 to 160 cm 3 / g. The term "polyamide" generally includes homopolyamides as well as copolyamides.

[0045] Semi-crystalline or amorphous polyamides or mixtures thereof are preferred.

[0046] Examples thereof are polyamides derived from lactams having 7 to 13 ring members, such as polycaprolactam, polycaprylolactam and polylaurolactam, such as PA6, PA12.

[0047] Further examples are polyamides obtained via the reaction of dicarboxylic acids with diamines.

[0048] Particularly suitable dicarboxylic acids are alkanedicarboxylic acids having 6 to 12, especially 6 to 10 carbon atoms, and aromatic dicarboxylic acids. By way of mere example, those that may be mentioned here are adipic acid, azelaic acid, sebacic acid, dodecanedioic acid and terephthalic acid and / or isophthalic acid.

[0049] Particularly suitable diamines are alkanediamines having 6 to 12, especially 6 to 8 carbon atoms, and furthermore 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.

[0050] Suitable polyamides are polyhexamethylene adipamide, polyhexamethylene sebacamide, and polycaprolactam, and also PA6 / 66 copolyamides, in particular those having a proportion of caprolactam units of 5 to 95% by weight (for example Ultramid® C31, manufactured by BASF SE).

[0051] Other suitable polyamides are obtained via direct polymerization, in the presence of water, from ω-aminoalkyl nitriles, such as aminocapronitrile (PA6) and adiponitrile and hexamethylenediamine (PA66), for example as described in German Patent Application Publication No. 10313681 (DE-A 10313681), European Patent Application Publication No. 1198491 (EP-A 1198491) and European Patent No. 922065 (EP 922065).

[0052] For example, polyamides obtained via the condensation of 1,4-diaminobutane and adipic acid at elevated temperature (PA46), or polyamides obtained via the condensation of hexamethylenediamine and sebacic acid (PA610) may be mentioned. Methods for producing polyamides of this structure are described, for example, in European Patent Application Publication No. 38094 (EP-A 38 094), European Patent Application Publication No. 38582 (EP-A 38 582), and European Patent Application Publication No. 39524 (EP-A 39 524).

[0053] Other suitable examples are polyamides obtained via the copolymerization of two or more of the abovementioned monomers, and mixtures in any desired mixing ratio of two or more polyamides. Mixtures of PA66 and other polyamides, in particular blends of PA6 and PA66, and PA6 / 66 copolyamides and PA66 / 6 copolyamides are particularly preferred.

[0054] Other copolyamides that have proven to be particularly advantageous are semi-aromatic copolyamides such as PA6 / 6T, PA6T / 6, PA6T / 66, and PA66 / 6T, where their triamine content is preferably less than 0.5% by weight, preferably less than 0.3% by weight (see European Patent Application Publication No. 299444 (EP-A 299 444)). Other polyamides resistant to high temperatures are known from European Patent Application Publication No. 1994075 (EP-A 19 94 075) (PA6T / 6I / MXD6).

[0055] The methods described in European Patent Application Publications Nos. 129195 and 129196 (EP-A 129 195 and 129196) can be used to produce preferred semi-aromatic polyamides with a low triamine content.

[0056] Other polyamides that have proven to be advantageous are aromatic polyamides such as PA9T, PA10T, PA4T, and copolyamides PA6I / 6T, PA6T / 6I.

[0057] Suitable copolyamides are A1) units derived from 20.0 to 90.0% by weight of terephthalic acid and hexamethylenediamine, A2) units derived from 0 to 50.0% by weight of ε-caprolactam, A3) units derived from 0 to 80.0% by weight of adipic acid and hexamethylenediamine, A4) 0 to 40.0% by weight of further polyamide-forming monomers and are composed of, and the proportion of component A2) or A3) or A4) or a mixture thereof is at least 10.0% by weight.

[0058] Component A1) contains units derived from 20.0 to 90.0% by weight of terephthalic acid and hexamethylenediamine.

[0059] In addition to units derived from terephthalic acid and hexamethylenediamine, the copolyamide optionally contains units derived from ε-caprolactam, and / or units derived from adipic acid and hexamethylenediamine, and / or units derived from further polyamide-forming monomers.

[0060] Aromatic dicarboxylic acid A4) contains 8 to 16 carbon atoms. Suitable aromatic dicarboxylic acids are, for example, isophthalic acid, substituted terephthalic acid and isophthalic acid, such as 3-t-butylisophthalic acid, polycyclic dicarboxylic acids, such as 4,4'- and 3,3'-diphenyldicarboxylic acid, 4,4'- and 3,3'-diphenylmethanedicarboxylic acid, 4,4'- and 3,3'-sulfodiphenylcarboxylic acid, 1,4- or 2,6-naphthalenedicarboxylic acid, phenoxyterephthalic acid, and isophthalic acid is particularly preferred.

[0061] Further polyamide-forming monomers A4) can be derived from dicarboxylic acids having 4 to 16 carbon atoms, and aliphatic or cycloaliphatic diamines having 4 to 16 carbon atoms, and further from aminocarboxylic acids / corresponding lactams having 7 to 12 carbon atoms. Examples of suitable monomers of those types mentioned are suberic acid, azelaic acid and sebacic acid (as representative examples 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 representative examples of diamines and caprolactam), enanthlactam, ω-aminoundecanoic acid and laurolactam (as representative examples of lactam / aminocarboxylic acids).

[0062] Suitable such copolyamides are described more specifically in German Patent Application Publication No. 102009011668 (DE-A-10 2009 011 668).

[0063] The following list includes, but is not comprehensive, the polyamides described above and other polyamides suitable for the purposes of this specification, and the monomers included: AB polymers: PA4 pyrrolidone PA6 ε-caprolactam PA7 ethanol lactam PA8 caprylolactam PA9 9-aminopelargonic acid PA11 11-aminoundecanoic acid PA12 laurolactam.

[0064] AA / BB polymers: PA46 tetramethylenediamine, adipic acid PA66 hexamethylenediamine, adipic acid PA69 hexamethylenediamine, azelaic acid PA610 hexamethylenediamine, sebacic acid PA612 hexamethylenediamine, decanedicarboxylic acid PA613 hexamethylenediamine, undecanedicarboxylic acid PA1212 1,12-dodecanediamine, decanedicarboxylic acid PA1313 1,13-diaminotridecane, undecanedicarboxylic acid PA4T tetramethylenediamine, terephthalic acid PA6T hexamethylenediamine, terephthalic acid PA9T 1,9-nonanediamine, terephthalic acid PA10T 1,10-decanediamine, terephthalic acid PAMXD6 m-xylylenediamine, adipic acid.

[0065] AA / BB polymers: PA6I hexamethylenediamine, isophthalic acid PA6-3-T trimethylhexamethylenediamine, terephthalic acid PA6 / 6T (see PA6 and PA6T) PA6T / 6 (see PA6T and PA6) PA6T / 66 (see PA6T and PA66) PA66 / 6T (see PA66 and PA6T) PA6 / 66 (see PA6 and PA66) PA66 / 6 (see PA66 and PA6) PA6 / 12 (see PA6 and PA12) PA66 / 6 / 610 (see PA66, PA6 and PA610) PA6T / 6I / 66 (see PA6T, PA6I and PA66) PA6I / 6T (see PA6I and PA6T) PA6T / 6I (see PA6I and PA6T) PAPACM12 diamino dicyclohexylmethane, laurolactam PA6I / 6T / PACM PA6I / 6T + as diamino dicyclohexylmethane PA12 / MACMI laurolactam, dimethyldiamino dicyclohexylmethane, isophthalic acid PA12 / MACMT laurolactam, dimethyldiamino dicyclohexylmethane, terephthalic acid PAPDA-T phenylenediamine, terephthalic acid.

[0066] Preferred polyamide A and further polyamide B are PA6, PA66, PA6 / 66, PA66 / 6, PA12, PA610, PA46, PA6T / 6, PA6T / 66, PA9T, PA10T, PA6I / 6T, PA6T / 6I, PA6T / 6I / 66, PA66 / 6T, and PA4T, more preferably PA6, PA66, PA6 / 66 or PA66 / 6, and mixtures thereof.

[0067] Preferably, polyamide A is a polyamide containing polyamide from post-industrial (= pre-consumer) and / or post-consumer waste from an extrusion process preferably selected from the group of blow molding, film extrusion, tube extrusion, sheet extrusion, spinning and combinations thereof.

[0068] The preferred polymer A comprises polyamide waste that has been selected, i.e., contains only polyamide as the polymer component. The polyamide may be a mixture of two or more different polyamides or one polyamide. Suitable polyamides are described above.

[0069] Preferably, the preferred polyamide A comprising polyamide from post-industrial (= pre-consumer) and / or post-consumer waste from an extrusion process selected from the group consisting of blow molding, film extrusion, tube extrusion, sheet extrusion, spinning, and combinations thereof, in one embodiment, may be used in the method of the present invention in combination with one or more residual filler materials and / or one or more residual additives present in the post-industrial (= pre-consumer) and / or post-consumer waste. The fillers and additives depend on the type of post-industrial (= pre-consumer) and / or post-consumer waste and are known to those skilled in the art.

[0070] One advantage of the method of the present invention is that the residual fillers and additives do not interfere with the method of the present invention.

[0071] However, the polyamide A used in the present invention is preferably used in the absence of a significant amount of residual filler material and / or additive (i.e., preferably, there is 5% by mass or less of residual filler material and 1% by mass or less of residual additive with respect to polyamide A), and more preferably, the polyamide A is used in the method of the present invention in the absence of residual filler material and / or additive.

[0072] In one embodiment, the polyamide A is preferably a polyamide (Aa) consisting of 100% polyamide from post-industrial and / or post-consumer waste from an extrusion process selected from the group consisting of blow molding, film extrusion, tube extrusion, sheet extrusion, spinning, and combinations thereof, or Aa Preferably, it is a polyamide (Aa) from post-industrial and / or post-consumer waste from an extrusion process selected from the group consisting of blow molding, film extrusion, tube extrusion, sheet extrusion, spinning and combinations thereof, Ab virgin polyamide (Ab) and a mixture therewith.

[0073] Therefore, preferably, polyamide A is Aa 50 to 100% by mass, preferably 80 to 100% by mass, more preferably 90 to 100% by mass of post-industrial and / or post-consumer waste (Aa) from an extrusion process selected from the group consisting of blow molding, film extrusion, tube extrusion, sheet extrusion, spinning and combinations thereof, Ab 0 to 50% by mass, preferably 0 to 20% by mass, more preferably 0 to 10% by mass of virgin polyamide (Ab), where the sum of the amounts of (Aa) and (Ab) is 100% by mass.

[0074] More preferably, polyamide A is Aa 100% by mass of post-industrial and / or post-consumer waste (Aa) from an extrusion process selected from the group consisting of blow molding, film extrusion, tube extrusion, sheet extrusion, spinning and combinations thereof including.

[0075] The above polyamide A is suitable as polyamides Aa and Ab.

[0076] The present invention makes it possible to provide injection molding of PA (polyamide B) using 100% recycled extrusion grade PA (polyamide A).

[0077] In the meaning of the present invention, "waste" means any substance or object that the holder discards or intends or needs to discard (definition of EU law).

[0078] Pre-consumer (= post-industrial) waste, in the meaning of the present application, originates from the manufacture of products, and post-consumer waste originates from its use.

[0079] "Recycling" means any recovery operation that reprocesses waste materials into products, materials or substances for the original or other purposes. It includes the reprocessing of organic materials, but does not include energy recovery, and reprocessing into materials used as fuel or for landfill operations (Article 3(17) of the Waste Framework Directive (WFD)).

[0080] The post-industrial (= pre-consumer) and / or post-consumer waste polyamides for the process of the present invention preferably originate from the extrusion industry, particularly the manufacture of fibres, sheets, films, tubes and profiles by extrusion.

[0081] According to the present application, one object of the present invention is to recycle post-industrial and / or post-consumer polyamide waste, particularly from the extrusion industry, polyamide A, to provide a recycled polyamide B having good flowability and sufficient melt stability for injection moulding applications.

[0082] Thus, polyamide B includes polyamides of the same type as polyamide A, but has a lower viscosity than polyamide A. Suitable classes of polyamides are described above.

[0083] However, post-industrial and / or post-consumer waste, preferably included in polyamide A and originating from the extrusion industry, has too high a viscosity to be reused in injection moulding applications. To reuse such materials in injection moulding applications, it is necessary to reduce the melt viscosity of the recycled material.

[0084] Accordingly, the present invention provides a method for reducing the viscosity of polyamide A by preferably keeping the ratio of the concentrations of the end groups (amino groups and carboxylic acid groups) of the starting polyamide A constant (with a deviation of about ±20%, preferably about ±10%). As a result, the melt stability (MVR over time) of the recycled polyamide B is ensured, which is a prerequisite for applying the recycled polymer, especially in injection molding, preferably at a low additive concentration.

[0085] The method of the present invention for producing polyamide B involves melt mixing polyamide A and a salt of a diacid and a diamine. Suitable polyamides A and B, and suitable salts C of a diacid and a diamine, as well as the amounts of the suitable salts of a diacid and a diamine, are described above.

[0086] In the method of the present invention, the melt mixing of polyamide A and the salt of a diacid and a diamine is carried out optionally in the presence of a filler material (D) and / or at least one further additive (E). When the filler material (D) and / or at least one further additive (E) is present, the polymer composition for injection molding containing the recycled polymer B is directly obtained by the method of the present invention without further processing steps. Suitable filler materials (D) and further additives (E) are described below.

[0087] In the above embodiment, polyamide A is preferably fed into an extruder and compounded optionally with at least one further additive (E) and / or filler material (E) to produce a grade of polyamide for injection molding. The addition according to the present invention of the salt of a diacid and a diamine in the first stage of extrusion results in a rapid and homogeneous reduction of the molecular weight of the recycled material via amide group transfer. Only a small amount of the salt of a diacid and a diamine (typically 1% or less, preferably 0.01 - 1% by weight, more preferably 0.1 - 0.9% by weight, most preferably 0.15% - 0.5% by weight) is required to efficiently reduce the viscosity of polyamide A.

[0088] The melt mixing is preferably carried out in an extruder. The extruder may be a single-screw, twin-screw or multi-screw extruder. A twin-screw extruder is preferred. A twin-screw extruder is also known as a double-screw extruder. The twin-screw extruder can rotate co-rotatingly or counter-rotatingly. Single-screw extruders, twin-screw extruders, and multi-screw extruders are known to those skilled in the art and are described, for example, in C. Rauwendaal: Polymer extrusion, Carl Hanser Verlag GmbH & Co. KG, 5th edition (January 16, 2014), pages 13 - 47.

[0089] The extruder may further include additional devices, such as mixing elements or kneading elements. Mixing elements serve to mix the individual components contained in the extruder. Suitable mixing elements are known to those skilled in the art and are, for example, static mixing elements or dynamic mixing elements. Kneading elements also serve to mix the individual components contained in the extruder. Suitable kneading elements are known to those skilled in the art and are, for example, kneading screws or kneading blocks, such as disk kneading blocks or shoulder kneading blocks.

[0090] The extruder is operated continuously or discontinuously, i.e., the method according to the invention is a continuous or discontinuous method.

[0091] In the melt mixing method of the present invention, the temperature of the extruder during melt mixing can be any temperature, usually in the range of 200 to 380 °C, preferably in the range of 220 to 350 °C, and particularly preferably in the range of 240 to 340 °C.

[0092] The barrel temperature of the extruder may be higher than the temperature of the components within the extruder, or it is also possible for the barrel temperature of the extruder to be lower than the temperature of the components within the extruder. For example, when the components are being heated, the barrel temperature of the extruder can initially be higher than the temperature of the components within the extruder. When the components within the extruder are being cooled, it is possible for the barrel temperature of the extruder to be lower than the temperature of the components within the extruder. The temperature shown in and regarding the extruder in the present invention means the barrel temperature of the extruder. "The barrel temperature of the extruder" means the temperature of the barrel of the extruder. Accordingly, the barrel temperature of the extruder is the temperature of the outer wall of the barrel of the extruder. As the extruder, any extruder known to those skilled in the art that can be used at the temperature and pressure during compounding is suitable. Generally, the extruder can be heated to at least the temperature at which polyamide A, the salt of a diacid and a diamine, and optionally at least one further additive (E) and / or filler material (D) are compounded.

[0093] Polyamide A, and the salt of a diacid and a diamine, and optionally at least one further additive (E) and / or filler material (D) can be added to the extruder continuously or simultaneously, and are mixed and compounded within the extruder to obtain polyamide B or the polyamide composition described below. In one preferred embodiment, the salt C of the diacid and the diamine is added to the polyamide in a first stage. In a second stage, optionally at least one further additive (E) and / or filler material (D) is added. The diacid and diamine of salt C are added to the extruder in the form of salt C, or alternatively, the diacid and diamine are added separately and salt C is formed within the extruder.

[0094] In the method according to the invention, polyamide A is melt-mixed with a salt of a diacid and a diamine. By said method, a polyamide B having a lower viscosity number than polyamide A is obtained. Strictly speaking, in the method of the invention, since the salt C of a diacid and a diamine is present together with polyamide A, polyamide B is formed which comprises the same units as polyamide A, selected from combinations of one or more diamines and one or more diacids, one or more lactams, and mixtures thereof, and furthermore units derived from the diacid and diamine forming salt C. If polyamide A contains units based on the same diacid and diamine as the diacid and diamine present in salt C, said units are indistinguishable, as is the case for example for polyamide 66 as polyamide A and salt C of adipic acid and hexamethylenediamine. However, if the units in polymer B derived from the diacid and diamine forming salt C are different from the units forming polyamide A, a polymer B1 is obtained which contains, in addition to the units already present in polymer A, a small amount of units derived from the diacid and diamine forming salt C. Since the viscosity of the polymer formed from the same units already present in polymer A is different from the viscosity of polymer A, i.e. a polymer different from polymer A is formed, said polymer is hereinafter referred to as polymer B * and is so designated.

[0095] Accordingly, the present invention further provides a) a polyamide B formed from units selected from combinations of one or more diamines and one or more diacids, one or more lactams, and mixtures thereof, from 99.00 to 99.99% by weight, preferably from 99.10 to 99.90% by weight, more preferably from 99.50 to 99.85% by weight * and b) units derived from the diacid and diamine forming salt C, from 0.01 to 1% by weight, preferably from 0.1 to 0.9% by weight, more preferably from 0.15 to 0.5% by weight comprising a polyamide B1, wherein the units derived from the diacid and diamine forming salt C are different from the units forming polyamide B * relates to said polyamide B1.

[0096] Preferred salt C is described above. More preferably, the diacid and diamine forming salt C are adipic acid and hexamethylenediamine.

[0097] Polyamide B * contains the same units as polyamide A, selected from the combination of one or more diamines and one or more diacids, one or more lactams, and mixtures thereof. The suitable units selected from the combination of one or more diamines and one or more diacids, one or more lactams, and mixtures thereof that form polyamide A, and thus also form polyamide B * are described above.

[0098] The ratio of the concentration of the amino terminal groups of polyamide B1 to the concentration of the carboxyl terminal groups of polyamide B is preferably 0.2 or more, more preferably 0.40 or more, and most preferably 0.70 or more.

[0099] Polyamide B1 is a subgroup of polyamide B. The only difference between polyamide B and polyamide B1 is that the units derived from the diacid and diamine forming salt C are different from the units derived from polyamide A (the units corresponding to the units forming polyamide B * ).

[0100] That is, polyamide B a) 99.00 to 99.99% by mass, preferably 99.10 to 99.90% by mass, more preferably 99.50 to 99.85% by mass, of units selected from the combination of one or more diamines and one or more diacids, one or more lactams, and mixtures thereof to form polyamide B * and b) 0.01 to 1% by mass, preferably 0.1 to 0.9% by mass, more preferably 0.15 to 0.5% by mass, of units derived from the diacid and diamine forming salt C and is composed of.

[0101] Therefore, the present invention further provides a) 99.00 to 99.99% by mass, preferably 99.10 to 99.90% by mass, more preferably 99.50 to 99.8% by mass of PA6, and b) units derived from salt C of adipic acid and hexamethylenediamine in an amount of 0.01 to 1% by mass, preferably 0.1 to 0.9% by mass, more preferably 0.15 to 0.5% by mass relates to polyamide B1 composed of

[0102] In a further embodiment, the present invention relates to polyamide B obtained by the method according to the present invention, wherein the ratio of the concentration of amino end groups of polyamide B to the concentration of carboxyl end groups of polyamide B is preferably 0.2 or more, more preferably 0.40 or more, and most preferably 0.70 or more.

[0103] The determination of the concentration of amino end groups and the concentration of carboxyl end groups is described above. Further, suitable polyamide B is described above.

[0104] The fine structure of polyamide B1 is different from that of polyamides obtained by a polymerization process as disclosed in, for example, JP-A-2001-200054, JP-A-09-234789, and WO 2018 / 165641, in which a polyamide-forming monomer, such as a caprolactam monomer, is polymerized in the presence of a salt of a diacid and a diamine, such as an equimolar salt of hexamethylenediamine and adipic acid.

[0105] As described in WO 2018 / 165641, a polyamide 6 / 66 copolymer formed substantially randomly from a caprolactam monomer and a hexamethylenediamine monomer is formed when the caprolactam monomer is polymerized in the presence of an equimolar salt of hexamethylenediamine and adipic acid (see, for example, paragraph

[0026] of WO 2018 / 165641).

[0106] However, polyamide B1 according to the present invention is polyamide B* (In the most preferred embodiment, it may be polyamide 6) and is composed of units derived from a diacid and a diamine that form 0.01 to 1% by mass of salt C (preferably a salt of adipic acid and hexamethylenediamine). Therefore, the polyamide B1 does not form a polyamide 6 / 66 copolymer in which units based on caprolactam and units based on hexamethylenediamine are randomly distributed.

[0107] Without being bound by theory, in the method of the present invention, certain dimers or oligomers are formed from salt C, which can then be predicted to be incorporated into polymer chain B * by an exchange reaction with polymer B * in polymer B1, the monomer units forming polymer B * and the monomer units based on salt C are not randomly distributed, and polyamide B1 contains end groups formed by salt C and blocks formed by dimers or oligomers formed from salt C.

[0108] Therefore, the microstructure of polyamide B1 is different from the microstructures of polyamides disclosed in, for example, JP 2001-200054 A, JP 09-234789 A, and WO 2018 / 165641.

[0109] The present invention further relates to (i) polyamide B1 or polyamide B according to the present invention, and (ii) optionally a filler material (D), and (iii) optionally at least one further additive (E) and relates to a polyamide composition containing at least one of one filler material (D) or one further additive (E).

[0110] Preferably, the polyamide composition (i) from 40 to 99.9% by mass, preferably from 50 to 99.75% by mass, more preferably from 60 to 99.5% by mass of polyamide B1 or polyamide B according to the present invention, and (ii) from 0 to 60% by mass, preferably from 0 to 50% by mass, more preferably from 0 to 40% by mass of a filler material (D), and (iii) from 0 to 25% by mass, preferably from 0 to 20% by mass, more preferably from 0 to 15% by mass of at least one further additive (E) containing, with at least one of one filler material (D) or one further additive (E) being present, when the filler material (D) is used, its minimum amount is preferably 10% by mass, more preferably 15% by mass, most preferably 20% by mass, and when a further additive (E) is used, its minimum amount is preferably 0.1% by mass, more preferably 0.25% by mass, most preferably 0.5% by mass, the total amount of components B1 or B, D and E is 100% by mass.

[0111] Polyamide B1 and polyamide B are described above.

[0112] The filler material (D) may include one or more of the fillers described below.

[0113] As component D, the polyamide composition contains from 0 to 60% by mass, preferably from 0 to 50% by mass, more preferably from 0 to 40% by mass of at least one filler material, which is generally a fibrous and / or particulate filler.

[0114] Preferably, component D includes glass fibers and is present in an amount of from 10 to 60% by mass, more preferably from 15 to 50% by mass, most preferably from 20 to 40% by mass.

[0115] When component D is present, the maximum amount of polyamide B1 or polyamide B is reduced by the minimum amount of component D, so that the total amount of components B1 or B, D and E remains 100% by mass.

[0116] The fibrous or particulate filler D that can be described is carbon fiber, glass fiber, glass beads, amorphous silica, calcium silicate, calcium metasilicate, magnesium carbonate, kaolin, chalk, powdered quartz, mica, barium sulfate, and feldspar.

[0117] Preferred fibrous fillers that can be described are carbon fiber, aramid fiber, and potassium titanate fiber, and glass fiber in the form of E-glass is particularly preferred. They can be used as rovings or in the form of commercially available chopped glass.

[0118] The fibrous filler can be surface-treated with a silane compound to improve its compatibility with the thermoplastic resin.

[0119] Suitable silane compounds have the general formula: (X-(CH2) n ) k -Si-(O-C m H 2m+1 ) 4-k wherein the definitions of the substituents are as follows: X is

Chemical formula

[0120] Preferred silane compounds are aminopropyltrimethoxysilane, aminobutyltriethoxysilane, aminopropyltriethoxysilane, and aminobutyltriethoxysilane, and furthermore, the corresponding silanes containing a glycidyl group as substituent X.

[0121] The amount of silane compound generally used for surface coating is 0.01 to 2% by mass, preferably 0.025 to 1.0% by mass, and particularly 0.05 to 0.5% by mass (relative to component D).

[0122] Needle-like mineral fillers are also suitable.

[0123] For the present invention, the needle-like mineral filler is a mineral filler having strongly developed needle-like characteristics. An example is needle-like wollastonite. The mineral preferably has an L / D (length to diameter) ratio of 8:1 to 35:1, preferably 8:1 to 11:1. The mineral filler can optionally be pretreated with the above-mentioned silane compound, but the pretreatment is not essential.

[0124] Other fillers that can be mentioned are kaolin, calcined kaolin, wollastonite, talc and chalk, and furthermore layered or needle-like nanofillers, and their amount is preferably 0.1 to 10%. Preferred materials for this purpose are boehmite, bentonite, montmorillonite, vermiculite, hectorite and laponite. The layered nanofillers are organically modified by prior art methods to improve their compatibility with organic binders. Adding layered or needle-like nanofillers to the nanocomposites of the present invention results in a further improvement in mechanical strength.

[0125] As component E, the polyamide composition of the present invention may contain 0 to 25% by mass, preferably 0 to 20% by mass, more preferably 0 to 15% by mass of at least one further additive. When component E is present, the maximum amount of polyamide B1 or polyamide B is reduced by the minimum amount of component E, so that the total amount of components B1 or B, D and E remains 100% by mass.

[0126] When at least one further additive is used, its minimum amount is preferably 0.1% by mass, more preferably 0.25% by mass, most preferably 0.5% by mass.

[0127] The composition of the present invention may contain, as component E, conventional processing aids, further stabilizers, oxidation retardants, agents for preventing thermal and ultraviolet light decomposition, lubricants and mold release agents, colorants such as dyes and pigments, nucleating agents, plasticizers, and the like.

[0128] The polyamide composition of the present invention may contain, as component E1, 0.05 to 3% by mass, preferably 0.1 to 1.5% by mass, and particularly 0.1 to 1% by mass of a lubricant.

[0129] Salts of Al, alkali metals, or alkaline earth metals, or esters or amides of fatty acids having 10 to 44 carbon atoms, preferably 12 to 44 carbon atoms, are preferred.

[0130] The metal ions are preferably alkaline earth metals and Al, and Ca or Mg is particularly preferred.

[0131] Preferred metal salts are Ca stearate and Ca montanate, and further Al stearate.

[0132] Mixtures of various salts in any desired mixing ratio can also be used.

[0133] The carboxylic acid can be monobasic or dibasic. Examples that can be mentioned are pelargonic acid, palmitic acid, lauric acid, margaric acid, dodecanedioic acid, behenic acid, and particularly preferably stearic acid, capric acid, and further montanic acid (a mixture of fatty acids having 30 to 40 carbon atoms).

[0134] The aliphatic alcohol can be monohydric to tetrahydric. Examples of the alcohol are n-butanol, n-octanol, stearyl alcohol, ethylene glycol, propylene glycol, neopentyl glycol, pentaerythritol, and glycerol and pentaerythritol are preferred.

[0135] Aliphatic amines can be mono-basic to tribasic. Examples thereof are stearylamine, ethylenediamine, propylenediamine, hexamethylenediamine, di(6-aminohexyl)amine, with ethylenediamine and hexamethylenediamine being particularly preferred. Preferred esters or amides are, correspondingly, glycerol distearate, glycerol tristearate, ethylenediamine distearate, glycerol monopalmitate, glycerol trilaurate, glycerol monobehenate, and pentaerythritol tetrastearate.

[0136] It is also possible to use mixtures of various esters or amides combined in any desired mixing ratio, or mixtures of esters and amides.

[0137] As component E, the polyamide composition according to the present invention may contain at least one heat stabilizer, preferably in an amount of 0.01% to 3% by mass, particularly preferably 0.02% to 2% by mass, especially 0.05% to 1.0% by mass, based on the total mass of the composition.

[0138] The heat stabilizer is preferably selected from copper compounds, secondary aromatic amines, sterically hindered phenols, phosphites, phosphonites, and mixtures thereof.

[0139] As component E, at least one sterically hindered phenol antioxidant in an amount of 0.05 to 3% by mass, preferably 0.1 to 2% by mass, particularly 0.1 to 1% by mass can be used.

[0140] This component E preferably has a molecular weight exceeding 500 g / mol, more preferably exceeding 1000 g / mol. Furthermore, component C should preferably exhibit high thermal stability, for example, in a TGA (thermogravimetric analysis) experiment (from 40°C to 120°C at 10°C / min, then isothermal for 15 minutes, followed by from 120°C to 600°C at 20°C / min) under nitrogen, showing a maximum weight loss of 5%, more preferably a maximum weight loss of 2%.

[0141] Component E has, as a steric hindrance group, at least one branched C3-C 12 -alkyl group-substituted phenol group, preferably at least one, more preferably at least two. The substituted phenol group is covalently bonded to the structure of component E.

[0142] Suitable sterically hindered phenol E is, in principle, all compounds having a phenol structure and having at least one bulky group on the phenol ring. Bulky groups are, for example, branched C3-C 12 -alkyl group, preferably a branched C3-C6-alkyl group, more preferably an isopropyl or tert-butyl group.

[0143] For example, the formula

Chemical formula

[0144] Antioxidants of the above types are described, for example, in German Patent Application Publication No. 2702661 (DE-A 27 02 661) (U.S. Patent No. 4360617 (US-A 4 360 617)).

[0145] Preferred sterically hindered phenols of the other group are provided by substituted phenylcarboxylic acids, especially those derived from substituted phenylpropionic acids, which preferably have at least one bulky group on the phenyl group. They preferably contain in their structure at least one, preferably two, covalently bonded substituted phenylcarboxylic acid units, which preferably have at least one bulky group on the phenyl group.

[0146] Preferred phenylcarboxylic acids are phenyl-C1-C 12 -carboxylic acids, more preferably phenyl-C2-C6-carboxylic acids. The phenyl group is preferably a phenol group having at least one bulky group on the phenol ring as shown above. Accordingly, the sterically hindered phenols described above are preferably covalently bonded to C1-C 12 -alkane carboxylic acids, more preferably straight-chain C2-C6-alkane carboxylic acids.

[0147] Particularly preferred compounds from this class are of the formula

Chemical formula

[0148] Preferred compounds corresponding to those formulas are

Chemical formula

[0149] All of the following should be described 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, manufactured by BASF SE), Distearyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 2,6,7-Trioxa-1-phosphabicyclo[2.2.2]oct-4-ylmethyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, 3,5-Di-tert-butyl-4-hydroxyphenyl-3,5-distearylthiotriazineamine, 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.

[0150] Compounds that have been proven to be particularly effective and are thus preferably used are 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 1,6-hexanediol bis(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (Irganox® 259), pentaerythrityl tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and furthermore N,N'-hexamethylenebis-3,5-di-tert-butyl-4-hydroxyhydrocinamide (Irganox® 1098), and in particular the products (trademarks) 245 and Irganox® 1010 manufactured by BASF SE as mentioned above, which have particularly good suitability.

[0151] In some cases, sterically hindered phenols that do not have one or more sterically hindering groups ortho to the phenolic hydroxy group have proven to be particularly advantageous when evaluating the color fastness during storage, especially under long-term diffused light.

[0152] Furthermore, it is advantageous to use sterically hindered phenol antioxidants that also have a sufficiently high molecular weight, preferably above 500 g / mol, especially above 1000 g / mol. Furthermore, they preferably exhibit a high thermal stability with less than 2% decomposition measured by TGA (thermogravimetric analysis) up to 300 °C under a nitrogen atmosphere.

[0153] The polyamide composition of the present invention may contain, as component E2, 0.05 to 3% by mass, preferably 0.1 to 1.5% by mass, and particularly 0.1 to 1% by mass of a copper stabilizer, preferably cuprous halide, especially in a mixture with an alkali metal halide, preferably KI, especially in a ratio of 1:4, or a sterically hindered phenol, or a mixture thereof.

[0154] Preferred salts of monovalent copper used are cuprous acetate, cuprous chloride, cuprous bromide, and cuprous iodide. The said materials contain them in an amount of 5 to 500 ppm of copper, preferably 10 to 250 ppm, based on the polyamide.

[0155] Advantageous properties are obtained in particular when copper is present in a molecular distribution in the polyamide. This is achieved when a concentrate in the form of a homogeneous solid solution, which contains polyamide, and a monovalent copper salt, and an alkali metal halide, is added to the molding composition. For example, a typical concentrate consists of 79 to 95% by mass of polyamide, and a mixture composed of 21 to 5% by mass of copper iodide or copper bromide and potassium iodide. The copper concentrate in the homogeneous solid solution is preferably 0.3 to 3% by mass, in particular 0.5 to 2% by mass, based on the total mass of the solution, and the molar ratio of cuprous iodide to potassium iodide is 1 to 11.5, preferably 1 to 5.

[0156] Suitable polyamides for the concentrate are homopolyamides and copolyamides, in particular PA6.

[0157] According to a preferred embodiment of the invention, the molding composition is copper-free, in particular free of copper stabilizers, such as Cu(I) halides, and combinations of Cu(I) halides and alkali metal halides.

[0158] More preferably, the thermoplastic molding composition of the invention is free of metal halides. Metal halide-free systems, so-called electrically friendly systems, are of great interest because electromobility, electrification and connectivity are on the increase in almost all industries.

[0159] Therefore, the polyamide composition is preferably free of metal halides, in particular Cu halides and alkali metal halides.

[0160] The polyamide composition of the invention may contain 0.001 to 10% by mass, preferably 0.05 to 5% by mass, in particular 0.1 to 2.5% by mass of iron powder having a particle size (d 50 value) of up to 10 μm. The iron powder is preferably obtained via the thermal decomposition of pentacarbonyl iron.

[0161] Iron exists in several allotropes: 1. α-Fe (ferrite) forms a body-centered cubic lattice, is magnetizable, dissolves a small amount of carbon, and exists as pure iron up to 928 °C. At 770 °C (Curie temperature), it loses its ferromagnetic properties and becomes paramagnetic, and iron in the temperature range of 770 - 928 °C is also called β-Fe. At room temperature and at least 13000 MPa of pressure, α-Fe becomes what is known as ε-Fe, with a volume reduction of about 0.20 cm 3 / mol and where the density increases from 7.85 to 9.1 (at 20000 MPa). 2. γ-Fe (austenite) forms a face-centered cubic lattice, is non-magnetic, dissolves a large amount of carbon, and is observable only in the temperature range of 928 - 1398 °C. 3. Body-centered cubic δ-Fe exists from 1398 °C to the melting point of 1539 °C.

[0162] Metallic iron is generally silver-white, with a density of 7.874 (heavy metal), a melting point of 1539 °C, a boiling point of 2880 °C, a specific heat (18 - 100 °C) of about 0.5 g -1 K -1 , and a tensile strength of 220 - 280 N / mm 2 . The above values correspond to chemically pure iron.

[0163] The industrial production of iron uses the refining of iron ore, iron slag, roasted pyrite or blast furnace dust, and the recycling of scrap and alloys.

[0164] The iron powder of the present invention is preferably produced via the thermal decomposition of pentacarbonyl iron at a temperature of 150 °C to 350 °C. The particles thus obtained preferably have a spherical shape and are thus spherical or approximately spherical (other names used are spherolitic).

[0165] Preferred iron powder has a particle size distribution as described below; the particle size distribution here is determined using laser scattering in a very dilute aqueous suspension (for example, using Beckmann LS13320). The particle sizes (and distributions) described hereinafter can optionally be obtained via grinding and / or sieving.

[0166] where d xx means that XX% of the total volume of the particles is less than the stated value. d 50 Value: maximum 10 μm, preferably 1.6 - 8 μm, particularly 2.9 - 7.5 μm, very particularly 3.4 - 5.2 μm, d 10 Value: preferably 1 - 5 μm, particularly 1 - 3 μm, and very particularly 1.4 - 2.7 μm, d 90 Value: preferably 3 - 35 μm, particularly 3 - 12 μm, and very particularly 6.4 - 9.2 μm.

[0167] The iron powder preferably has an iron content of 97 - 99.8 g / 100 g, preferably 97.5 - 99.6 g / 100 g. The content of other metals is preferably less than 1000 ppm, particularly less than 100 ppm, and very particularly less than 10 ppm.

[0168] The Fe content is usually determined via infrared spectroscopy.

[0169] The carbon content is preferably 0.01 - 1.2 g / 100 g, preferably 0.05 - 1.1 g / 100 g, and particularly 0.4 - 1.1 g / 100 g. This carbon content in the preferred iron powder corresponds to that of the powder not reduced using hydrogen after the pyrolysis step.

[0170] The carbon content is usually determined by a method based on ASTM E1019, by burning the sample in an oxygen stream and then detecting the residual CO2 gas using IR (using Leco CS230 or CS - mat 6250, manufactured by Juwe).

[0171] The nitrogen content is preferably at most 1.5 g / 100 g, preferably 0.01 - 1.2 g / 100 g.

[0172] The oxygen content is preferably at most 1.3 g / 100 g, preferably 0.3 - 0.65 g / 100 g.

[0173] N and O are determined by heating the sample in a graphite furnace to about 2100 °C. Here, the oxygen obtained from the sample is converted to CO and measured by an IR detector. The N released from the N-containing compounds under the reaction conditions is discharged together with the carrier gas and detected and recorded by a TCD (thermal conductivity detector) (both methods are based on ASTM E1019).

[0174] The tapped density is preferably 2.5 - 5 g / cm 3 , particularly 2.7 - 4.4 g / cm 3 This generally means the density when the powder is filled, for example, into a container and compressed by vibration. Further preferred iron powders can be surface-coated with iron phosphate, ferrous phosphite, or SiO2.

[0175] The BET surface area according to DIN ISO 9277 is preferably 0.1 - 10 m 2 / g, particularly 0.1 - 5 m 2 / g, and preferably 0.2 - 1 m 2 / g, and particularly 0.4 - 1 m 2 / g.

[0176] To achieve particularly good dispersion of the iron particles, a masterbatch containing a polymer can be used. Polymers suitable for this purpose are polyolefins, polyesters, or polyamides, where it is preferred that the polymer of the masterbatch is the same as component A. The mass fraction of iron in the polymer is generally 15 - 80 mass%, preferably 20 - 40 mass%.

[0177] UV stabilizers that can generally be used in amounts up to 2% by weight based on the polyamide composition can be variously substituted resorcinols, salicylates, benzotriazoles, and benzophenones. Nigrosine can also be used.

[0178] Materials that can be added as colorants are inorganic pigments such as titanium dioxide, ultramarine, iron oxide, and carbon black, and also organic pigments such as phthalocyanine, quinacridone, perylene, and also dyes such as anthraquinone.

[0179] Materials that can be used as nucleating agents are sodium phenylphosphinate, aluminum oxide, silicon dioxide, and also, preferably, talc.

[0180] The polyamide composition may further contain a flame retardant as component E.

[0181] As component E, the polyamide composition may contain at least one phosphazene of general formula (IX) or (X) as a flame retardant in an amount of 1.0 to 10.0% by weight, preferably 2.0 to 6.0% by weight, particularly 3.0 to 5.0% by weight.

[0182] The minimum amount of this component E (flame retardant) is at least 1.0% by weight, preferably 2.0% by weight, particularly 3.0% by weight.

[0183] The maximum amount of this component E (flame retardant) is 10.0% by weight, preferably 6.0% by weight, particularly 5.0% by weight.

[0184] "Phosphazene" is a cyclic phosphazene of general formula (IX)

Chemical formula

Chemical formula

[0185] The production of such phosphazenes is described in European Patent Application Publication No. 0945478 (EP-A 0 945 478).

[0186] The cyclic phenoxyphosphazene of formula P3N3C of formula (XI) 36

Chemical formula

[0187] or the linear phenoxyphosphazene according to formula (XII)

Chemical formula

[0188] The phenyl group can be optionally substituted. The phosphazenes related to this application are described in Mark, J.E., Allcock, H.R., West, R., Inorganic Polymers, Prentice Hall, 1992, pages 61 to 141.

[0189] ​Cyclic phenoxyphosphazenes having at least three phenoxyphosphazene units are preferably used as component E. The corresponding phenoxyphosphazenes are described, for example, in paragraphs

[0051] to

[0053] of US Patent Application Publication No. 2010 / 0261818 (US 2010 / 0261818). In particular, formula (I) therein can be referred to. The corresponding cyclic phenoxyphosphazenes are further described in European Patent Application Publication No. 2100919 (EP-A-2 100 919), in particular in paragraphs

[0034] to

[0038] thereof. The production can be carried out as described in paragraph

[0041] of European Patent Application Publication No. 2100919. In one embodiment of the present invention, the phenyl groups in the cyclic phenoxyphosphazene can be substituted by C1-C4-alkyl groups. The case of pure phenyl groups is preferred.

[0190] For further description of cyclic phenoxyphosphazenes, reference can be made to the Roempp Chemie Lexikon, 9th edition, under the entry "Phosphazene". The production is carried out, for example, via cyclophosphazene obtained from PCl5 and NH4Cl, where the chlorine groups of the cyclophosphazene are replaced by phenoxy groups by reaction with phenol.

[0191] Cyclic phenoxyphosphazene compounds can be produced as described, for example, in Allcock, H.R., Phosphorus-Nitrogen Compounds (Academic Press, 1972), and in Mark, J.E., Allcock, H.R., West, R., Inorganic Polymers (Prentice Hall, 1992).

[0192] Component E is preferably a mixture of cyclic phenoxyphosphazenes having 3 and 4 phenoxyphosphazene units. The mass ratio of the ring containing 3 phenoxyphosphazene units to the ring containing 4 phenoxyphosphazene units is preferably about 80:20. Larger rings of phenoxyphosphazene units may also be present, but in small amounts. A suitable cyclic phenoxyphosphazene is obtained from Fushimi Pharmaceutical Co., Ltd. under the name Rabitle® FP-100. This is a matte white / yellowish solid having a melting point of 110°C, a phosphorus content of 13.4%, and a nitrogen content of 6.0%. The proportion of the ring containing 3 phenoxyphosphazene units is at least 80.0% by mass.

[0193] The polyamide composition may preferably contain, as a flame retardant, 1.0 to 6.0% by mass, preferably 2.5 to 5.5% by mass, particularly 3.0 to 5.0% by mass of at least one aliphatic or aromatic ester of phosphoric acid or polyphosphoric acid.

[0194] For this reason, phosphoric acid esters having a melting point of 70°C to 150°C, particularly those that do not move as solids, are preferred. This results in the product being easy to meter and showing significantly less movement in the molding material. Particularly preferred examples are commercially available phosphoric acid esters such as PX-200 (CAS: 139189-30-3) manufactured by Daihachi Chemical Industry Co., Ltd. or Sol-DP manufactured by ICL-IP. Further phosphoric acid esters having appropriate substituents on the phenyl group may be considered if it is possible to achieve a preferred melting range. The general structural formula is as follows, depending on the substitution pattern at the ortho or para position in the aromatic ring:

Chemical formula

[0195] Specific examples include PX-200:

Chemical formula

[0196] It is particularly preferred when at least one aromatic ester of polyphosphoric acid is used. Such an aromatic polyphosphoric acid ester is obtained, for example, under the trade name PX-200 from Daihachi Chemical Industry Co., Ltd.

[0197] As component E, the polyamide composition according to the present invention may contain, as a flame retardant, 5.0 to 30.0% by mass, preferably 10.0 to 25.0% by mass, particularly 12.0 to 20.0% by mass, for example about 16.0% by mass of at least one of the metal phosphinates or phosphinates described below.

[0198] Examples of preferred flame retardants for component E are metal phosphinates derived from hypophosphorous acid. For example, metal salts of hypophosphorous acid and Mg, Ca, Al or Zn as metals can be used. Here, aluminum hypophosphite is particularly preferred.

[0199] The phosphinate of formula (I) and / or the diphosphinate of formula (II) or their polymers

Chemical formula

[0200] Preferably, R 1 , R 2 are the same or different and represent hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl and / or phenyl.

[0201] Preferably, R 3 represents methylene, ethylene, n-propylene, isopropyl, 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.

[0202] Particularly preferably, R 1 , R 2 are hydrogen, methyl, ethyl, and M is Al, and aluminum hypophosphite is particularly preferred.

[0203] The production of phosphinates is preferably carried out by precipitating the corresponding metal salts from an aqueous solution. However, phosphinates can also be precipitated in the presence of suitable inorganic metal oxides or sulfides (white pigments such as TiO2, SnO2, ZnO, ZnS, SiO2) as carrier materials. This thus results in surface-modified pigments that can be used as laser-markingable flame retardants for thermoplastic polyesters.

[0204] Compared to hypophosphorous acid, metal salts of substituted phosphinic acids are preferably used in which one or two hydrogen atoms are replaced by phenyl, methyl, ethyl, propyl, isobutyl, isooctyl, or the group R’-CH-OH is replaced by R’-hydrogen, phenyl, tolyl. The metal is preferably Mg, Ca, Al, Zn, Ti, Fe. Aluminum diethylphosphinate (DEPAL) is particularly preferred.

[0205] For the description of phosphinates or diphosphinates, reference may be made to German Patent Application Publication No. 19960671 (DE-A 199 60 671), and furthermore German Patent Application Publication No. 4430932 (DE-A 44 30 932) and German Patent Application Publication No. 19933901 (DE-A 199 33 901).

[0206] Further flame retardants are, for example, halogen-containing flame retardants.

[0207] Suitable halogen-containing flame retardants are preferably brominated compounds such as brominated diphenyl ethers, brominated trimethylphenyl indane (FR 1808, manufactured by DSB), tetrabromobisphenol A, and hexabromocyclododecane.

[0208] Suitable flame retardants are preferably brominated compounds such as the structural formula

Chemical formula

[0209] Formula:

Chem.

[0210] The preferred brominated compounds further include the reaction product of an oligomer of tetrabromobisphenol A and an epoxide (n > 3) (for example, FR 2300 and 2400, manufactured by DSB) having the formula:

Chem.

[0211] The brominated oligostyrene preferably used as a flame retardant has an average degree of polymerization (number average) of 3 to 90, preferably 5 to 60, as measured by the vapor pressure osmometry method in toluene. Cyclic oligomers are also suitable. In a preferred embodiment of the present invention, the brominated oligomer styrene has the following formula I, wherein R represents hydrogen or an aliphatic group, particularly an alkyl group, such as CH2 or C2H5, and n represents the number of repeating chain-forming blocks. R 1 may be H or bromine or a fragment of a normal free radical former:

Chem.

[0212] ​The value of n may be from 1 to 88, preferably from 3 to 58. The brominated oligomer styrene contains 40.0 to 80.0% by mass, preferably 55.0 to 70.0% by mass of bromine. A product mainly composed of polydibromostyrene is particularly preferred. The substance is meltable without decomposition and is soluble, for example, in tetrahydrofuran. The substance can be produced either by ring bromination of (optionally aliphatically hydrogenated) styrene oligomers such as those obtained by thermal polymerization of styrene (according to DT-OS2537385), or by free radical oligomerization of suitable brominated styrenes. The production of the flame retardant may also be carried out by ionic oligomerization of styrene and subsequent bromination. The amount of brominated oligostyrene required to impart flame retardant properties to the polyamide depends on the bromine content. The bromine content in the molding material according to the present invention is 2.0 to 30.0% by mass, preferably 5.0 to 12.0% by mass.

[0213] The brominated polystyrene according to the present invention is typically obtained by the method described in European Patent Application Publication No. 047549 (EP-A 047 549):

Chemical formula

[0214] The brominated polystyrene obtainable by this method and commercially available brominated polystyrenes are mainly ring-substituted tribrominated products. n' (see III) generally has a value of 125 to 1500, which corresponds to a molecular weight of 42500 to 235000, preferably 130000 to 135000.

[0215] The bromine content (based on the content of ring-substituted bromine) is generally at least 50.0% by mass, preferably at least 60.0% by mass, and particularly 65.0% by mass.

[0216] Commercially available powdery products generally have a glass transition temperature of 160°C to 200°C and are obtained, for example, under the names SAYTEX® HP-7010 (manufactured by Albemarle) and Pyrocheck® PB 68 (manufactured by Ferro Corporation).

[0217] A mixture of brominated oligostyrene and brominated polystyrene can also be used in the molding material according to the present invention, and the mixing ratio can be freely selected.

[0218] Chlorine-containing flame retardants are also suitable, and Declorane Plus® (manufactured by OxyChem) is preferred.

[0219] Suitable halogen-containing flame retardants are preferably cyclic brominated polystyrene, brominated polybenzyl acrylate, brominated bisphenol A epoxy oligomer or brominated bisphenol A polycarbonate.

[0220] In one embodiment of the present invention, a halogen-containing flame retardant is not used in the polyamide composition according to the present invention.

[0221] The flame-retardant melamine compound suitable as component E in the present invention is a melamine compound that, when added to a glass fiber-filled polyamide molding material, reduces flammability and has a flame-retardant effect on flame behavior, thereby improving the properties in the UL94 test and the glow wire test.

[0222] The melamine compound is selected, for example, from melamine borate, melamine phosphate, melamine sulfate, melamine pyrophosphate, melam, melem, melon, melamine cyanurate, or a mixture thereof.

[0223] Melamine cyanurate preferably suitable according to the present invention is a reaction product of preferably equimolar amounts of melamine (Formula I) and cyanuric acid / isocyanuric acid (Formulas Ia and Ib).

[0224] [Chemistry]

[0225] It can be obtained, for example, by reacting an aqueous solution of the starting compound at 90 °C to 100 °C. Commercially available products are white powders having an average particle size d of 1.5 to 7 μm 50 and a d 99 value of less than 50 μm.

[0226] More suitable compounds (often described as salts or adducts) are melamine sulfate, melamine, melamine borate, oxalate, primary phosphate, secondary phosphate and dipyrophosphate, melamine borate neopentyl glycol. According to the present invention, the molding material is preferably free of melamine phosphate of the polymer (CAS No. 56386-64-2 or 218768-84-4).

[0227] This is to be understood as meaning a melamine polyphosphate of a 1,3,5-triazine compound having a 1,3,5-triazine content of a 1,3,5-triazine compound with an average degree of condensation n of 20 to 200 and 1.1 to 2.0 moles of phosphorus atoms per mole. Preferably, the n value of such a salt is generally 40 to 150, and the proportion of the 1,3,5-triazine compound per mole of phosphorus atom is preferably 1.2 to 1.8. Further, the pH of a 10% aqueous slurry of a salt produced according to European Patent No. 095030 (EP-B1 095 030) generally exceeds 4.5 and is preferably at least 5.0. The pH is typically determined by adding 25 g of the salt and 225 g of clean water to a 300 ml beaker at 25°C, stirring the resulting aqueous slurry for 30 minutes, and then measuring the pH. The above-mentioned n value, number average degree of condensation, can be determined by solid state NMR of 31P. J.R. van Wazer, C.F. Callis, J. Shoolery and R. Jones, J. Am. Chem. Soc., 78, 5715, 1956 disclose that the number of adjacent phosphate groups results in unique chemical shifts, thereby clearly distinguishing orthophosphate, pyrophosphate and polyphosphate.

[0228] Suitable guanidine salts are

Table 1

[0229] Regarding the present invention, "compounds" are to be understood as meaning not only, for example, benzoguanamine itself and their adducts / salts, but also nitrogen-substituted derivatives and their adducts / salts.

[0230] Ammonium polyphosphate (NH4PO3) n [wherein n is about 200 to 1000, preferably 600 to 800], and formula IV [Chemical formula] Tris(hydroxyethyl)isocyanurate (THEIC), or aromatic carboxylic acids Ar(COOH) which may optionally be present as mixtures with each other m [wherein Ar represents a monocyclic, bicyclic or tricyclic aromatic six-membered ring system, and m is 2, 3 or 4] are also suitable reaction products.

[0231] Examples of suitable carboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, 1,3,5-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, pyromellitic acid, mellophanic acid, prehnitic acid, 1-naphthoic acid, 2-naphthoic acid, naphthalenedicarboxylic acid, and anthracenecarboxylic acid.

[0232] Production is carried out according to the method in European Patent Application Publication No. 584567 (EP-A 584 567) by reacting tris(hydroxyethyl)isocyanurate with an acid, its alkyl ester or its halide.

[0233] Such reaction products are mixtures of esters of monomers or oligomers which may be crosslinked. The degree of oligomerization is typically from 2 to about 100, preferably from 2 to 20. A mixture of THEIC and / or its reaction product with a phosphorus-containing nitrogen compound, especially (NH4PO3) n or melamine pyrophosphate or polymeric melamine phosphate is preferably used. For example, (NH4PO3) n The mixing ratio of (NH4PO3) to THEIC is preferably 90.0 to 50.0:10.0 to 50.0, especially 80.0 to 50.0:50.0 to 20.0 by mass% based on the mixture of such compounds.

[0234] Formula V [Chemical formula] [wherein, R and R’ each represents a linear or branched alkyl group having 1 to 10 carbon atoms, preferably hydrogen] The benzoguanidine compounds, and in particular the adducts thereof with phosphoric acid, boric acid and / or pyrophosphoric acid are also suitable flame retardants.

[0235] Formula VI

Chemical formula

Chemical formula

[0236] Suitable products are commercially available or can be obtained according to German Patent Application Publication No. 19614424 (DE-A 196 14 424).

[0237] The cyanoguanidine (formula VIII) useful according to the present invention can be obtained, for example, by reacting calcium cyanamide with a carboxylic acid, and the resulting cyanamide dimerizes at pH 9 to pH 10 to form cyanoguanidine.

[0238]

Chemical formula

[0239] Commercially available products are white powders having a melting point of 209°C to 211°C.

[0240] It is particularly preferred to use melamine cyanurate (for example, Melapur® MC25, manufactured by BASF SE).

[0241] It is also further possible to use other metal oxides, such as antimony trioxide, antimony pentoxide, sodium antimonate and similar metal oxides. However, the use of such metal oxides is preferably avoided because they are already present in component F. For the description of pentabromobenzyl acrylate and antimony trioxide or antimony pentoxide, reference can be made to European Patent Application Publication No. 0624626 (EP-A 0 624 626).

[0242] It is also possible to use phosphorus, such as red phosphorus, as a flame retardant. Red phosphorus can be used, for example, in the form of a masterbatch.

[0243] Formula

Chemical formula

[0244] Preferred dicarboxylates contain Cl or bromine or hydrogen, independently of one another, as the R 1 ~R 4 groups, particularly preferably all R 1 ~R 4 groups are Cl and / or Br.

[0245] Be, Mg, Ca, Sr, Ba, Al, Zn, Fe are preferred as metal M.

[0246] Such dicarboxylates are commercially available or can be produced according to the method described in US Patent No. 3,354,191.

[0247] Functional polymers can also be used as component E. They can be, for example, flame-retardant polymers. Such polymers are described, for example, in US Patent No. 8,314,202 and include repeating units of 1,2-bis[4-(2-hydroxyethoxy)phenyl]ethanone. A more suitable functional polymer for increasing the amount of carbon residue is poly(2,6-dimethyl-1,4-phenylene oxide) (PPPO).

[0248] The present invention further preferably comprises the following steps: · Converting polyamide B or polyamide B1 that can be obtained or is obtained by the method according to the present invention to obtain a polymer product The present invention relates to a method for producing a polymer product, comprising.

[0249] The method preferably includes one or all of the additional steps of the method of the present invention for producing the above polyamide B or polyamide B1.

[0250] Preferably, the polymer product is a granule, strand, rod, plate, tube, foil, layer, film, sheet, fiber, filament, coating, extruded and / or molded part, soft foam, semi-rigid foam and / or rigid foam. More preferably, the polymer product is an injection molded part.

[0251] Accordingly, the present invention more preferably relates to a method for producing a molded article, comprising injection molding a polyamide B or polyamide B1 or polyamide composition according to the present invention.

[0252] Accordingly, the present invention further relates to a polymer product comprising the polyamide B or polyamide B1 or polyamide composition according to the present invention, said polymer product being preferably granules, strands, rods, plates, tubes, foils, layers, films, sheets, fibers, filaments, coatings, extruded and / or molded parts, soft foams, semi-rigid foams and / or rigid foams. More preferably, the polymer product is an injection molded part.

[0253] Preferably, the present invention relates to an injection molded part comprising the polyamide B or polyamide B1 or polyamide composition according to the present invention.

[0254] The present invention further relates to the use of a polymer product comprising the polyamide B or polyamide or polyamide composition according to the present invention for producing a polymer product selected from granules, strands, rods, plates, tubes, foils, layers, films, sheets, fibers, filaments, coatings, extruded and / or molded parts, soft foams, semi-rigid foams and rigid foams. More preferably, the polymer product is an injection molded part.

[0255] Preferably, the present invention relates to the use of the polyamide B or polyamide B1 or this polyamide composition according to the present invention for producing an injection molded part.

[0256] Even more preferably, the polymer product produced by the method of the present invention preferably comprises a semi-crystalline or amorphous polyamide or a mixture thereof selected from one or more elements of the group consisting of PA6, PA66, PA6 / 66, PA66 / 6, PA12, PA610, PA46, PA6T / 6, PA6T / 66, PA9T, PA10T, PA6I / 6T, PA6T / 6I, PA6T / 6I / 66, PA66 / 6T and PA4T, more preferably selected from one or more elements of the group consisting of PA6, PA66, PA6 / 66 and PA66 / 6.

[0257] The polymer product is preferably · Parts of motor vehicles, preferably cylinder head covers, engine covers, housings for charge air coolers, flaps of charge air coolers, intake pipes, intake manifolds, connectors, gear wheels, fan wheels, cooling water boxes, housings for heat exchangers or housing parts, coolant coolers, charge air coolers, thermostats, water pumps, radiators, fixing parts or components of battery systems for electromobility, dashboards, steering column switches, seats, headrests, center consoles, transmission parts, door modules, exterior vehicle bodywork for A, B, C or D pillar covers, spoilers, door handles, exterior mirrors, front windscreen wipers, front windscreen wiper protection housings, decorative grilles, cover strips, roof rails, window frames, sunroof frames, antenna panels, headlights and taillights, engine covers, cylinder head covers, intake manifolds, airbags or cushions, · Fabrics, preferably shirts, trousers, pullovers, boots, shoes, soles, tights, or jackets, · Electrical components, preferably passive or active electrical or electronic components, printed circuit boards, housing members, foils, lines, switches, plugs, sockets, distributors, relays, resistors, capacitors, inductors, coils, lamps, diodes, LEDs, transistors, connectors, regulators, integrated circuits (ICs), processors, controllers, memories, sensors, connectors, microswitches, microbuttons, semiconductors, reflector housings for light-emitting diodes (LEDs), fasteners, spacers, bolts, strips, slide-in guides, screws, nuts, film hinges, snap hooks (snap-ins) or spring tongues for electrical or electronic components, · Consumer products and / or pharmaceutical products, preferably tennis strings, climbing ropes, bristles, brushes, artificial turf, 3D printing filaments, lawn mowers, zippers, surface fasteners, fabrics for paper-making machines, extrusion coatings, fishing lines, fishing nets, offshore lines and ropes, vials, syringes, ampoules, bottles, sliding parts, spindle nuts, chain conveyors, plain bearings, rollers, wheels, gears, rollers, ring gears, screws and spring dampers, hoses, pipelines, cable sheaths, sockets, switches, cable ties, fan wheels, carpets, boxes or bottles for cosmetics, mattresses, cushions or heat insulators, and / or · Packages for the food industry, preferably single-layer or multi-layer inflation films, cast films (single-layer or multi-layer), biaxially stretched films, laminated films or a part thereof.

[0258] The present invention further relates to a method and a polymer product of the present invention, wherein the content of polyamide A in the polymer product is generally 1% by mass or more, preferably 2% by mass or more, more preferably 5% by mass or more, more preferably 15% by mass or more, more preferably 30% by mass or more, more preferably 40% by mass or more, more preferably 60% by mass or more, more preferably 80% by mass or more, more preferably 90% by mass or more, more preferably 95% by mass or more, and / or the content of polyamide A in the polymer product is generally 100% by mass or less, preferably 95% by mass or less, more preferably 90% by mass or less, more preferably 50% by mass or less, more preferably 25% by mass or less, more preferably 10% by mass or less, and, preferably, the content is specified based on a chain model of identity retention and / or segregation and / or mass balance and / or book and claim management, preferably mass balance, preferably based on the International Sustainability Carbon Certification (ISCC) standard.

[0259] The conversion step for obtaining the polymer product can include one or more synthesis steps and can be carried out by conventional syntheses and techniques well known to those skilled in the art. Independently of the person skilled in the art who evaluates the novelty and inventive step of the independent claims, the person skilled in the art carrying out the conversion step is a person from the technical field of the depolymerization and / or synthesis and / or production of monomers, polymers and polymer compounds, and their further processing (such as extrusion, injection molding). Examples of the conversion step are described in "Industrial Organic Chemistry", Volume 3, Wiley-VCH, 1997; ISBN: 978-3-527-28838-0; "Kunststoffhandbuch", Volume 11, Subvolume 17, Carl Hanser Verlag, in particular Volume 6, "Polyamide", 1st Edition, 1966; "Injection Molding Reference Guide", 4th Edition, CreateSpace Independent Publishing Platform, 2011, ISBN: 978-1466407824; International Publication No. 2008 / 155271 (WO 2008 / 155271 (A1)) and International Publication No. 2013 / 139827 (WO 2013139827 (A1)), each of which is incorporated herein by reference.

[0260] The polyamide B, polyamide B1 and polyamide compositions according to the invention are particularly useful for injection molding.

[0261] Accordingly, the present invention relates to injection molded parts comprising the polyamide B, polyamide B1 and polyamide compositions according to the invention.

[0262] Examples of injection-molded parts according to the present invention are injection-molded parts for automobiles, electronic devices, chemical apparatuses, machines, etc. Almost all parts of a vehicle, such as engine parts, electrical parts, and body parts, are included in the injection-molded parts according to the present invention. Engine parts include, inter alia, the intake system and the fuel system, such as the cylinder head cover of the engine, the throttle, the casing of the air filter unit, the air horn of the vehicle, the air-conditioning hose of the vehicle, the cooling fan and its casing, the inlet pipe, the brake oil tank, and the filler. Body parts include, inter alia, the fender of the automobile, the frame of the rearview mirror, the bumper, the instrument panel, the cargo bed, the door handle, the wiper bracket, the buckle of the seat belt, and various decorative parts in the vehicle. Electrical devices in the vehicle include, inter alia, electric control doors and windows, connectors, the crisp box, and cable ties.

[0263] The present invention further relates to a method for manufacturing a molded article, which includes the use of polyamide B, polyamide B1, and the polyamide composition according to the present invention for manufacturing injection-molded parts, and injection-molding the polyamide B, polyamide B1, and the polyamide composition according to the present invention. Examples of suitable injection-molded parts are described above.

[0264] The present invention will be further illustrated by the following examples.

Examples

[0265] Manufacture of polyamide B and polyamide composition containing polyamide B Viscosity measurement The viscosity number (VN) of the polyamide and the polyamide composition according to the present invention is measured in sulfuric acid in accordance with EN ISO 307:2019 (in 96 mass% [m / m] sulfuric acid at 25 °C, 0.5% [m / v] polyamide).

[0266] The melt volume flow rate (MVR) of the polyamide according to the present invention is measured in accordance with Procedure A of EN ISO 1133-1:2011. The material is melted in a heated cylinder and extruded into the open space by a piston through a nozzle under a defined pressure. Test conditions: 275 °C / 5 kg, and the material contains less than 0.05% water. The volume of the extrudate is measured as a function of time (Table 1 (below), after 5 minutes, 10 minutes, and 30 minutes).

[0267] The concentration of amino end groups (AEG [meq / kg]) of the polyamide disclosed in the present invention is measured by potentiometric titration of a polyamide-methanol-phenol solution with an aqueous hydrochloric acid solution. The concentration of carboxyl end groups (CEG [meq / kg]) of the polyamide disclosed in the present invention is measured by titrating a polyamide-benzyl alcohol solution with an alcoholic potassium hydroxide solution.

[0268] Examples 1C, 2C and 3 - 6 The components described in Table 1 were compounded in the ratios shown in the table. In Examples 3 - 6 of the present invention, the ratio of Ultramid B33 to the AH salt was varied. In Comparative Example 1C, the AH salt was not used, and in Comparative Example 2, PDMA was used instead of the AH salt. A twin-screw extruder MC / 26 / 2 manufactured by Coperion was used at a temperature of 300 / 320 / 320 / 320 / 330 / 330 / 330 / 330 / 330 / 330 / 330 / 330 °C at 50 kg / hour, 500 rpm and 12 zones. All additives were added by Coldfeed, and the glass fiber was added in zone 5.

[0269] [Table 2]

[0270] Only in the examples of the present invention, a reduction in the viscosity number VN is achieved, the polyamide composition is suitable for injection molding, and a significant increase in MVR over time is avoided.

[0271] *means a comparative example. 1) Ultramid B33 (i.e., Ultramid B33 01) is a medium-viscosity polyamide 6 grade manufactured by BASF SE; 2) ChopVantage® HP 3610, manufactured by Nippon Electric Glass; 3) N,N'-ethylenebisstearamide, manufactured by Lonza; 4) 20% CuI / KI (1 / 3) in 80% Ultramid® B27; Ultramid® B27 is a low-viscosity polyamide 6 grade manufactured by BASF; 5) 30% Cabot Corporation's carbon black Black Pearls® 880 in 70% Lyondellbasell's Lupolen® 1800H; Lupolen 1800H is a low-density polyethylene resin; 6) hexamethylenediamine adipate (salt of adipic acid and hexamethylenediamine); 7) pyromellitic dianhydride.

Claims

1. A method for producing polyamide B, comprising melt-mixing polyamide A and a salt C of a diacid and a diamine, wherein the polyamide B has a viscosity number measured in sulfuric acid according to EN ISO 307:2019 that is lower than that of the polyamide A, and the ratio of the concentration of amino end groups of polyamide B to the concentration of amino end groups of polyamide A, measured by potentiometric titration of a polyamide-methanol-phenol solution with an aqueous hydrochloric acid solution, the ratio of the concentration of carboxyl end groups of polyamide B to the concentration of carboxyl end groups of polyamide A, measured by titrating a polyamide-benzyl alcohol solution with an alcoholic potassium hydroxide solution is 0.8 to 1.2 in polyamide B, said method.

2. The ratio of the concentration of amino end groups of polyamide B, measured by potentiometric titration of a polyamide-methanol-phenol solution with an aqueous hydrochloric acid solution, to the concentration of carboxylic acid end groups of polyamide B, measured by titrating a polyamide-benzyl alcohol solution with an alcoholic potassium hydroxide solution is 0.2 or more, preferably 0.40 or more, more preferably 0.70 or more, the method according to claim 1.

3. The method according to claim 1 or 2, wherein the salt C of the diacid and the diamine is present in an amount of 0.01 to 1% by mass, preferably 0.1 to 0.9% by mass, based on polyamide A.

4. The method according to any one of claims 1 to 3, wherein the salt C of the diacid and the diamine is hexamethylenediamine adipate.

5. The viscosity number of polyamide A is 120 to 250 cm 3 / g, preferably 150 to 220 cm 3 / g, more preferably 170 to 210 cm 3 / g, and the method according to any one of claims 1 to 4.

6. The viscosity number of polyamide B is 80 to 200 cm 3 / g, preferably 100 to 180 cm 3 / g, more preferably 120 to 160 cm 3 / g, and the method according to any one of claims 1 to 5.

7. The polyamide A is preferably a semi-crystalline or amorphous polyamide or a mixture thereof selected from one or more elements of the group consisting of PA6, PA66, PA6 / 66, PA66 / 6, PA12, PA610, PA46, PA6T / 6, PA6T / 66, PA9T, PA10T, PA6I / 6T, PA6T / 6I, PA6T / 6I / 66, PA66 / 6T and PA4T, more preferably selected from one or more elements of the group consisting of PA6, PA66, PA6 / 66 and PA66 / 6, the method according to any one of claims 1 to 6.

8. The method according to any one of claims 1 to 7, wherein the polyamide A preferably comprises post-industrial and / or post-consumer waste from an extrusion process selected from the group consisting of blow molding, film extrusion, tube extrusion, sheet extrusion, spinning, and combinations thereof.

9. The method according to any one of claims 1 to 8, wherein the polyamide A consists of post-industrial and / or post-consumer waste.

10. The method according to any one of claims 1 to 9, wherein the melt mixing is carried out in the presence of a filler (D) and / or a further additive (E).

11. A method for producing a polymer product, preferably comprising the steps according to any one of claims 1 to 10, the following steps: - Converting the polyamide B obtainable or obtained by the method according to any one of claims 1 to 10 to obtain a polymer product The method as described above, wherein the polymer product is preferably granules, strands, rods, plates, tubes, foils, layers, films, sheets, fibers, filaments, coatings, extruded and / or molded parts, soft foams, semi-rigid foams and / or rigid foams.

12. The content of the polyamide B in the polymer product is 1% by mass or more, preferably 2% by mass or more, more preferably 5% by mass or more, more preferably 15% by mass or more, more preferably 30% by mass or more, more preferably 40% by mass or more, more preferably 60% by mass or more, more preferably 80% by mass or more, more preferably 90% by mass or more, more preferably 95% by mass or more, and / or The content of the polyamide B in the polymer product is 100% by mass or less, preferably 95% by mass or less, more preferably 90% by mass or less, more preferably 50% by mass or less, more preferably 25% by mass or less, more preferably 10% by mass or less, and Preferably, the content is specified based on a chain model of identity retention and / or segregation and / or mass balance and / or book and claim management, preferably based on mass balance, preferably based on the International Sustainability Carbon Certification (ISCC) standard, according to the method described in claim 15.

13. The ratio of the concentration of amino end groups of polyamide B, measured by potentiometric titration of a polyamide-methanol-phenol solution with an aqueous hydrochloric acid solution, to the concentration of carboxylic acid end groups of polyamide B, measured by titrating a polyamide benzyl alcohol solution with an alcoholic potassium hydroxide solution, is preferably 0.2 or more, more preferably 0.40 or more, and most preferably 0.70 or more. Polyamide B obtained by the method according to any one of claims 1 to 10.

14. c) Polyamide B formed from units selected from combinations of one or more diamines and one or more diacids, one or more lactams, and mixtures thereof, in an amount of 99.00 to 99.99% by mass, preferably 99.10 to 99.90% by mass * and d) units derived from a diacid and a diamine forming salt C in an amount of 0.01 to 1% by weight, preferably 0.1 to 0.9% by weight A polyamide B1 composed of, wherein units derived from a diacid and a diamine forming a salt C are different from the units forming polyamide B * The polyamide B1 described above.

15. Polyamide B1 according to claim 14, wherein the diacid and diamine forming salt C are adipic acid and hexamethylenediamine.

16. The viscosity number of polyamide B is 80 to 200 cm 3 / g, preferably 100 to 180 cm 3 / g, more preferably 120 to 160 cm 3 / g, the polyamide B according to claim 13, or the polyamide B1 according to claim 14 or 15.

17. The polyamide B * is preferably a semi-crystalline or amorphous polyamide or a mixture thereof selected from one or more elements of the group consisting of PA6, PA12, PA610, PA46, PA6T / 6, PA9T, PA10T, PA6I / 6T, PA6T / 6I, and PA4T, more preferably PA6, the polyamide B1 according to any one of claims 14 to 16.

18. (i) polyamide B according to claim 13 or 16, or polyamide B1 according to any one of claims 14 to 17, and (ii) optionally a filler material (D), and (iii) optionally at least one further additive (E) A polyamide composition comprising at least one of one filler material (D) or one further additive (E) is present.

19. A polymer product comprising the polyamide B according to claim 13 or 16, or the polyamide B1 according to any one of claims 14 to 17, or the polyamide composition according to claim 18, wherein the polymer product is preferably granules, strands, rods, plates, tubes, foils, layers, films, sheets, fibers, filaments, coatings, extruded and / or molded parts, soft foams, semi-rigid foams and / or rigid foams. Said polymer product.

20. Use of the polyamide B according to claim 13 or 16, or the polyamide B1 according to any one of claims 14 to 17, or the polyamide composition according to claim 18, for producing a polymer product selected from granules, strands, rods, plates, tubes, foils, layers, films, sheets, fibers, filaments, coatings, extruded and / or molded parts, soft foams, semi-rigid foams and rigid foams.

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