CH718923A2 - Flame retardant, partially aromatic polyamides. - Google Patents

Abstract

The present invention relates to inherently flame-retardant, partially aromatic polyamides with the polyamide units AB/AC/AE/DB/DC/DE/F, where at least the polyamide units AC must be present, the polyamide units AB, AE, DB, DC, DE and F are optional and wherein the monomer units A, B, C, D, E and F are derived from the following molecules which are amidically bound in the polyamide X: A: Acyclic aliphatic diamines; B: Phosphorus-free aromatic dicarboxylic acids; C: phosphorus-containing, aromatic dicarboxylic acids of the formulas 1 to 3 D: cycloaliphatic diamines or diamines with aromatic structural units; E: Aliphatic dicarboxylic acids F: Aminocarboxylic acids, lactams. The invention also relates to flame-retardant molding compositions based on inherently flame-resistant, partially aromatic polyamides.

Description

The present invention relates to inherently flame-retardant, partially aromatic polyamides based on aliphatic diamines and phosphorus-containing aromatic dicarboxylic acids and optionally other polyamide-forming components. The invention also relates to flame-retardant molding compositions based on inherently flame-resistant, partially aromatic polyamides. Both the polyamides and the molding compositions produced from them have good flame retardancy and good mechanical properties. These molding compounds are suitable for producing particularly thin-walled moldings for the electrical and electronics industry, such as housings, housing components or connectors. Furthermore, the invention relates to the use of the polyamides and polyamide molding compounds according to the invention for the production of moldings, in particular components for the electrical and electronics industry and for the automobile industry.

[0002] For some uses, high demands are placed on plastics with regard to their flame-retardant properties. Because of the risk of short circuits, it is essential that plastics are flame-retardant, particularly when used in electrical or electronic devices.

In addition to plastics that are flame-retardant per se (= inherent flame retardancy) and plastics coated with a flame retardant, plastics with a reactive flame retardant are also used, i.e. the flame retardant is part of the plastic and was chemically bonded to it during polymerization. Another way to make plastics flame-retardant is to compound them with flame-retardant additives. Common additives include nitrogen-based compounds such as melamine and urea, brominated polystyrenes, and organophosphorus compounds.

Another essential requirement for plastics are good mechanical properties, which can be further improved by fiber reinforcement, among other things. In the field of polyamides, the prior art contains a number of examples of glass-fiber-reinforced, flame-retardant molding compositions. Achieving fire protection class UL 94 V0 represents a particular challenge for glass fiber reinforced polyamide molding compounds.

It is also important that the flame-retardant polyamides and polyamide molding compounds can be easily processed, e.g.

[0006] EP 1 670 862 A1 relates to filler-containing, halogen-free flame-retardant molding compositions based on mixtures of aliphatic and partly aromatic polyamides which contain salts of phosphinic acids as flame retardants. The invention also relates to the use of the polyamide molding compounds according to the invention for the production of molded articles, in particular components for the electrical and electronics industry. However, the particulate flame retardants used lead to a reduction in the mechanical properties, in particular with regard to the stress at break, the elongation at break, the impact and notched impact properties, a deterioration in the surface quality and corrosion of the plant parts used for production and processing.

CN 101 735 455 A describes a process for the preparation of aromatic polyoxadiazoles from terephthalic acid, hydrazine and modified isophthalic acid in a solvent and wet-spun, flame-resistant, high-temperature-resistant fibers therefrom. The modified isophthalic acid has chloro, bromo, or diphenylphosphine oxide or diphenylphosphine sulfide substituents.

US Pat. No. 4,837,394 relates to electrostatic toner particles based on a polyester resin which contains, among other things, a dimethyl isophthalate provided with a phosphonium substituent as a monomer. The quaternary phosphonium groups act as charge carriers in the toner particles. Due to the homogeneous distribution of the charge carriers, a very low content of quaternary phosphonium groups in the range from 10 -9 to 10 -4 mol/g is already sufficient to implement an electrostatographic imaging process. However, this does not achieve adequate flame protection.

US Pat. No. 3,108,991 discloses linear polyamides based on bis(aminoalkyl)alkylphosphines and aliphatic or aromatic dicarboxylic acids and aliphatic diamines and bis(carboxyalkyl)alkylphosphine oxides. The polyamides described are soluble in cold or warm water and have low softening points.

US 2,646,420 relates to oriented fibers based on linear condensation polymers containing phosphorus in the polymer chain. In addition to good dyeability, the fibers also have good mechanical properties, in particular high green strength and good resilience. In the examples, the phosphorus-containing monomer used is bis(carboxyphenyl)methylphosphine oxide, which is condensed with various glycols or decanediamine.

The field of textile fibers is also related to document US Pat. No. 4,032,517 B, which comprises copolyamides containing 0.5 to 7.5% by weight of phosphorus as an integral part of the polymer chains. Bis(carboxyethyl)alkylphosphine oxides, which are polycondensed with hexanediamine and adipic acid, are proposed as phosphorus-containing dicarboxylic acids. The fibers should be permanently antistatic, moisture-regulating and flame-resistant.

WO 2018 071 790 A1 discloses flame-retardant polyamides that contain phosphorus in the polymer chain. The bis(4-methoxycarbonylphenoxy)phenylphosphine oxide used as the phosphorus-containing monomer is prepared from methylparaben and phenylphosphonic acid dichloride. The reaction of this phosphorus-containing dicarboxylic acid with m-xylylenediamine (MXDA) is described. Such a polyamide with 5 wt.

[0013] JP11286545A describes phosphorus-containing copolyamides with a high glass transition temperature, which can be prepared by polycondensation in an inert solvent at temperatures of 50 to 200.degree. 2,5-Dicarboxyphenylphosphonic acid, 3,5-dicarboxyphenylphosphinic acid and derivatives thereof are mentioned as the phosphorus-carrying monomer. The copolyamides worked in the examples based on the dicarboxyphenylphosphinic acids mentioned and the diamine 4,4'-oxydianiline and isophthalic acid as a further dicarboxylic acid have glass transition temperatures in the range from 240 to 276° C. and cannot be polycondensed in the melt.

The inherently flame-retardant polyamides described above in the prior art, which contain phosphorus in the polymer chain, have poor chemical resistance, are largely even soluble in cold or warm water, contain a "weak" C-P or C-O-P bond in the Polymer chain and usually have low softening temperatures, especially low glass transition temperatures and thus a rather low heat resistance. Others can only be prepared in solution.

PRESENTATION OF THE INVENTION

It is an object of the present invention, among other things, to avoid these disadvantages known from the prior art and to provide inherently flame-retardant polyamides and polyamide molding compositions produced therefrom which are characterized by good mechanical and thermal properties, good surface quality, are characterized by high temperature resistance and high flame retardancy. Preferably, the aim is for the polyamides and polyamide molding compounds according to the invention to have a fire protection classification V0 according to UL94 for specimens with a thickness of 0.35 to 3.2 mm, in particular 0.5 mm.

This object is achieved according to the invention on the one hand by a polyamide X with the polyamide units AB/AC/AE/DB/DC/DE/F according to claim 1, where at least the polyamide units AC must be present, the polyamide units AB, AE, DB , DC, DE and F are optional and the monomer units A, B, C, D, E and F are derived from the following molecules, which are amidically bound in the polyamide X:

A: Acyclic aliphatic diamines;

B: phosphorus-free aromatic dicarboxylic acids;

C: Phosphorus-containing, aromatic dicarboxylic acids according to formula 1, 2 and/or 3, where the substituents R1, R2 are each independently C1-C8-alkyl or aryl and the substituents R3, R4, R5 are each independently H, alkyl, aryl , F, Cl, Br or P(R1)(R2)O;

D: cycloaliphatic diamines or diamines with aromatic structural units;

E: Aliphatic dicarboxylic acids

F: α,ω-aminocarboxylic acids, lactams.

The aromatic dicarboxylic acids of component B are different from the dicarboxylic acids of component C, in particular they are free of phosphorus.

The polyamide units mentioned above, e.g. the polyamide units AC, are to be understood as repeating units in the polyamide X. In the simplest case, the polyamide X is therefore a homopolyamide AC, which has only the repeating units AC, or a copolyamide AC, which has at least two different repeating units AC. In the latter case, at least two different acyclic diamines A or at least two different aromatic dicarboxylic acids C were used in the production of polyamide X.

The object is also achieved by a process for producing the polyamides according to the invention according to claim 9.

The object is also achieved by providing a polyamide molding composition FM according to claim 10, containing the polyamide X described above, and at least one filler and/or at least one additive and/or at least one polyamide Y different from polyamide X.

[0027] This object is further achieved by the moldings according to claim 13, which are formed at least partially from a polyamide X or the molding composition FM.

Finally, this object is achieved by using the polyamides X according to the invention and by using the polyamide molding compounds FM according to the invention as claimed in claim 15.

DEFINITIONS OF TERMS

For the purposes of the present invention, the term “polyamide” (abbreviation PA) is understood to be a generic term which includes homopolyamides and copolyamides regardless of their molar mass or viscosity. The generic term polyamide thus encompasses both the low-molecular polyamide precondensates and the post-condensed, high-molecular homo- and copolyamides. The chosen spellings and abbreviations for polyamides and their monomers correspond to those specified in ISO standard 16396-1 (2015(D)). The abbreviations used therein are used in the following synonyms for the IUPAC names of the monomers, in particular the following abbreviations for monomers occur: T or TPS for terephthalic acid, I or IPS for isophthalic acid, MACM for bis(4-amino-3-methylcyclohexyl)methane ( also referred to as 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, CAS No. 6864-37-5), PACM for bis(4-aminocyclohexyl)methane (also referred to as 4,4'-diaminodicyclohexylmethane, CAS no. No. 1761-71-3), TMDC for Bis(4-amino-3,5-dimethylcyclohexyl)methane (also referred to as 3,3',5,5'-Tetramethyl-4,4'-diaminodicyclohexylmethane, CAS -No. 65962-45-0). The abbreviation HMDA is used below for 1,6-hexanediamine (also referred to as hexamethylenediamine).

Compared to the partially crystalline polyamides, amorphous polyamides have no heat of fusion or only a very low heat of fusion that can hardly be detected. In dynamic differential calorimetry (DSC) according to ISO 11357 (2013) at a heating rate of 20 K/min, the amorphous polyamides preferably show a heat of fusion of less than 5 J/g, particularly preferably a maximum of 3 J /g, most preferably from 0 to 1 J/g. Amorphous polyamides do not have a melting point due to their amorphous nature.

In addition to a glass transition temperature, partially crystalline polyamides have a pronounced melting point and preferably show a heat of fusion of at least 15 J in differential scanning calorimetry (DSC) according to ISO 11357 (2013) at a heating rate of 20 K/min /g, more preferably at least 20 J/g, most preferably in the range of 25 to 80 J/g.

With regard to the inventive polyamide X, the monomers of the dicarboxylic acid and diamine component and any aminocarboxylic acids or monofunctional regulators used form, by condensation, repeating units or end groups in the form of amides, which are derived from the respective monomers. These generally make up at least 95 mol %, in particular at least 99 mol %, of all the repeating units and end groups present in the polyamide. In addition, the polyamide can also contain small amounts of other repeating units, which can result from degradation or side reactions of the monomers, for example the diamines.

The polyamide according to the invention is a polyamide X with the polyamide units AB/AC/AE/DB/DC/DE/F, where at least the polyamide units AC must be present. This means that the polyamide units AB, AE, DB, DC, DE and F are optional and, in the simplest case, the polyamide X exclusively comprises the polyamide units AC. The monomer units A, B, C, D, E and F are derived from the following bifunctional molecules, the monomers, which are amidically bound in the polyamide X.

The monomers for the production of the polyamides X comprise at least the following components A and C, which form the polyamide units AC, and optionally the components B, D, E and F: A acyclic aliphatic diamines, preferably acyclic aliphatic diamines with 6 to 12 carbon atoms; B at least one phosphorus-free aromatic dicarboxylic acid, preferably isophthalic acid, terephthalic acid or a mixture thereof; C phosphorus-containing, aromatic dicarboxylic acids according to formula 1, formula 2 and/or formula 3, where the substituents R1, R2 are each independently C1 - C8-alkyl or aryl and the substituents R3, R4, R5 are each independently H, alkyl, aryl, F, Cl, Br or P(R1)(R2)O; D cycloaliphatic diamines or diamines with an aromatic structural unit; E aliphatic dicarboxylic acids, preferably acyclic aliphatic dicarboxylic acids having 6 to 18 carbon atoms; F α,ω-aminocarboxylic acids, lactams.

If only a single acyclic aliphatic diamine A and a single phosphorus-containing, aromatic dicarboxylic acid C are selected as monomers, the polyamide X is composed of only one polyamide unit AC as a so-called repeating unit. If two or more different diamines A and/or at least two different dicarboxylic acids C are selected, the resulting polyamide X contains two or more different polyamide units AC as repeating units.

It is preferred if the total diamines used and the total dicarboxylic acids used in the polyamide X in a molar ratio of 1.05: 1 to 1: 1.05, particularly preferably from 1.03: 1 to 1: 1.03 and particularly preferably in the molar ratio of 1:1 in the polyamide X.

According to a preferred embodiment, the acyclic aliphatic diamine A is selected from the group consisting of 2-methyl-1,5-pentanediamine, hexanediamine, in particular 1,6-hexanediamine, 2,2,4-trimethyl-1,6-hexamethylenediamine, 2,4,4-trimethyl-1,6-hexamethylenediamine, nonanediamine, especially 1,9-nonanediamine, 2-methyl-1,8-octanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine and mixtures thereof. Particular preference is given to the acyclic, aliphatic diamines A selected from the group consisting of diamines having 6 to 12 carbon atoms, in particular 1,6-hexanediamine, 1,9-nonanediamine, 1,10-decanediamine and mixtures thereof.

Aromatic dicarboxylic acids are preferably selected as component B from the group consisting of terephthalic acid, isophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 3,3'-diphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid , 4,4'-diphenylmethanedicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid, 4,4'-diphenylisopropylidonedicarboxylic acid, 1,2-bis(phenoxy)ethane-4,4'-dicarboxylic acid, 2,5-anthracenedicarboxylic acid, 4,4 '-p-Terphenylenedicarboxylic acid and 2,5-pyridinedicarboxylic acid are used. The aromatic dicarboxylic acids B are particularly preferably selected as a mixture of isophthalic acid and terephthalic acid, the molar ratio of isophthalic acid to terephthalic acid preferably being at least 1.5, particularly preferably at least 1.8 and particularly preferably 1.8 to 2.5.

According to a further preferred embodiment, the phosphorus-containing, aromatic dicarboxylic acid C is selected from the group consisting of 3,5-dicarboxyphenyldiphenylphosphine oxide, 3,5-dicarboxyphenyldimethylphosphine oxide, 3,5-dicarboxyphenyldiethylphosphine oxide, 2,4-dicarboxyphenyldiphenylphosphine oxide, 2,4-dicarboxyphenyldimethylphosphine oxide, 2 ,4-dicarboxyphenyldiethylphosphine oxide. In particular, as the dicarboxylic acid, C 3,5-dicarboxyphenyldiphenylphosphine oxide is preferred.

A further preferred embodiment of the present invention provides that the diamines D are selected from the group consisting of cycloaliphatic diamines and diamines with aromatic structural units. The diamines D are preferably selected from the group consisting of bis(4-amino-3-methylcyclohexyl)methane (MACM), bis(4-aminocyclohexyl)methane (PACM), bis(4-amino-3-ethylcyclohexyl) methane, bis-(4-amino-3,5-dimethylcyclohexyl)-methane (TMDC), 2,6-norbornanediamine (2,6-bis-(aminomethyl)-norbornane), 1,3-diaminocyclohexane, 1,4- Diaminocyclohexanediamine, isophoronediamine, 1,3-bis-(aminomethyl)cyclohexane (BAC), 1,4-bis-(aminomethyl)cyclohexane, 2,2-(4,4'-diaminodicyclohexyl)propane, m-xylylenediamine (MXDA), p-xylylenediamine (PXDA) and mixtures thereof. The diamines D are particularly preferably selected from the group consisting of bis(4-amino-3-methylcyclohexyl)methane (MACM), bis(4-aminocyclohexyl)methane (PACM), m-xylylenediamine, p-xylylenediamine and mixtures of this.

A further preferred embodiment of the present invention provides that the aliphatic dicarboxylic acids E are selected from the group consisting of cyclohexane-1,3-dicarboxylic acid, cyclohexane-1,4-dicarboxylic acid, adipic acid, 1,7-heptanedioic acid, 1,8 -octanedioic acid, 1,9-nonanedioic acid, 1,10-decanedioic acid, 1,11-undecanedioic acid, 1,12-dodecanedioic acid, 1,13-tridecanedioic acid, 1,14-tetradecanedioic acid, 1,15-pentadecanedioic acid, 1,16-hexadecanedioic acid , 1,17-heptadecanedioic acid, 1,18-octadecanedioic acid, and mixtures thereof. The acyclic, aliphatic dicarboxylic acids E are particularly preferably selected from the group consisting of dicarboxylic acids having 6 to 16 carbon atoms, in particular adipic acid, 1,10-decanedioic acid, 1,12-dodecanedioic acid, 1,14-tetradecanedioic acid, 1,16-hexadecanedioic acid and cyclohexane -1,3-dicarboxylic acid, cyclohexane-1,4-dicarboxylic acid and mixtures thereof.

According to a further preferred embodiment of the present invention, the α,ω-aminocarboxylic acids or the lactams F are selected from the group consisting of caprolactam, undecanolactam, laurolactam, α,ω-aminocaproic acid, α,ω-aminoheptanoic acid, α,ω-aminooctanoic acid, α,ω-aminononanoic acid, α,ω-aminodecanoic acid, α,ω-aminoundecanoic acid (AUA) and α,ω-aminododecanoic acid (ADA), particular preference being given to α,ω-aminoundecanoic acid, caprolactam and laurolactam and mixtures thereof.

Furthermore, the polyamides X can contain at least one monofunctional carboxylic acid G1 or monofunctional amine G2 as monofunctional regulator G in copolymerized form. The monofunctional regulators G are used for the end-capping of the polyamides produced according to the invention. In principle, all monocarboxylic acids G1 which are capable of reacting with at least some of the available amino groups under the reaction conditions of the polyamide condensation are suitable. Suitable monocarboxylic acids G1 are aliphatic monocarboxylic acids, alicyclic monocarboxylic acids and aromatic monocarboxylic acids. These include formic acid, acetic acid, propionic acid, n-, iso- or tert-butyric acid, valeric acid, trimethylacetic acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, cyclohexanecarboxylic acid, benzoic acid , methylbenzoic acids, α-naphthoic acid, β-naphthoic acid, phenylacetic acid, oleic acid, ricinoleic acid, linoleic acid, linolenic acid, erucic acid, acrylic acid, methacrylic acid, and mixtures thereof. The monocarboxylic acid G1 is particularly preferably selected from acetic acid, propionic acid, benzoic acid, stearic acid and mixtures thereof. In a special embodiment, the aliphatic polyamides X contain exclusively acetic acid in copolymerized form as the monocarboxylic acid G1.

The polyamides X can contain at least one monoamine G2 in copolymerized form. The monoamines G2 are used for the end-capping of the polyamides produced according to the invention. In principle, all monoamines which are capable of reacting with at least some of the available carboxylic acid groups under the reaction conditions of the polyamide condensation are suitable. Preferred monoamines G2 are aliphatic monoamines. These include methylamine, ethylamine, propylamine, butylamine, hexylamine, heptylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, cyclohexylamine, dicyclohexylamine, and mixtures thereof.

The polyamide units AC or the polyamide units AC and DC are preferably 1 to 100 mol%, more preferably 5 to 80 mol% and particularly preferably 10 to 60 mol%, each based on a polyamide X with the Polyamide units AB/AC/AE/DB/DC/DE/F contained in polyamide X. The concentration specification of 100 mol% applies to cases in which the phosphorus-containing dicarboxylic acid C is contained exclusively in the polyamide units AC or exclusively in the polyamide units AC and DC.

Also preferred is a polyamide X in which, with regard to components A to F, at least one of the selection groups mentioned below is selected, preferably the selection groups for components A and C, particularly preferably the selection groups for components A, B and C and particularly preferably all selection groups are selected at the same time: A: the acyclic aliphatic diamines are selected from the group consisting of 1,6-hexanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,12-dodecanediamine, preferably selected as 1 ,6-hexanediamine or 1,10-decanediamine; B: the aromatic dicarboxylic acids are selected from the group consisting of terephthalic acid, isophthalic acid and mixtures thereof, preferably selected as a mixture of terephthalic acid and isophthalic acid; C: the phosphorus-containing, aromatic dicarboxylic acids are selected from the group consisting of 3,5-dicarboxyphenyldiphenylphosphine oxide, 3,5-dicarboxyphenyldimethylphosphine oxide, 3,5-dicarboxyphenyldiethylphosphine oxide, 2,4-dicarboxyphenyldiphenylphosphine oxide, 2,4-dicarboxyphenyldimethylphosphine oxide, 2, 4-dicarboxyphenyldiethylphosphine oxide, preferably selected from 3,5-dicarboxyphenyldiphenylphosphine oxide, 3,5-dicarboxyphenyldimethylphosphine oxide or 3,5-dicarboxyphenyldiethylphosphine oxide, particularly preferably selected from 3,5-dicarboxyphenyldiphenylphosphine oxide; D: the cycloaliphatic diamines and the diamines with aromatic structural units are selected from the group consisting of bis-(4-amino-3-methylcyclohexyl)methane (MACM), bis(4-aminocyclohexyl)methane (PACM), bis-(4- amino-3,5-dimethyl-cyclohexyl)methane (TMDC), m-xylylenediamine, p-xylylenediamine, and mixtures thereof; E: the aliphatic dicarboxylic acids are selected from the group consisting of adipic acid, 1,10-decanedioic acid, 1,12-dodecanedioic acid, 1,14-tetradecanedioic acid, 1,16-hexadecanedioic acid, cyclohexane-1,3-dicarboxylic acid, cyclohexane-1, 4-dicarboxylic acid and mixtures thereof;. F: the α,ω-aminocarboxylic acids or the lactams F are selected from the group consisting of α,ω-aminoundecanoic acid, caprolactam and laurolactam and mixtures thereof.

In a preferred embodiment, the polyamide X is a polyamide which comprises at least the polyamide units AB and AC.

In a particularly preferred embodiment, the polyamide X is a polyamide which comprises at least the polyamide units AB and AC and the monomer units A, B and C are derived from the following molecules which are amide-bonded in the polyamide X present: A: Acyclic aliphatic diamine selected from the group consisting of 1,6-hexanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,12-dodecanediamine; B: Aromatic dicarboxylic acid selected from the group consisting of terephthalic acid, isophthalic acid, and mixtures thereof; C: Phosphorus-containing aromatic dicarboxylic acid selected from the group consisting of 3,5-dicarboxyphenyldiphenylphosphine oxide, 3,5-dicarboxyphenyldimethylphosphine oxide, 3,5-dicarboxyphenyldiethylphosphine oxide, 2,4-dicarboxyphenyldiphenylphosphine oxide, 2,4-dicarboxyphenyldimethylphosphine oxide, 2,4-dicarboxyphenyldiethylphosphine oxide.

Preference is also given to a polyamide X in which the polyamide units AB are selected from the group consisting of the polyamide units 61, 6T, 81, 8T, 91, 9T, 101, 10T, 121, 12T, 6I/6, 6T/ 6, 9I/6, 9T/6, 10I/6, 10T/6, 12I/6, 12T/6, 6I/12, 6T/12, 9I/12, 9T/12, 10I/12, 10T/12, 12I/12, 12T/12, 6I/6T, 9I/9T, 10I/10T, 12I/12T.

Preference is given to a polyamide X which comprises at least the polyamide units AB and AC and where the content of the polyamide unit AB is 1 to 99 mol%, preferably 10 to 95 mol%, particularly preferably 40 to 90 mol% and where the The content of the polyamide units AC is 1 to 99 mol %, preferably 5 to 90 mol %, particularly preferably 10 to 60 mol %, based in each case on the sum of the polyamide units AB and AC.

In particular, a polyamide X is preferred in which the polyamide units AB are composed as follows: a1 60 to 100 parts by weight, preferably 60 to 80 parts by weight, particularly preferably 67 parts by weight of polyamide units AB which differ from Derive isophthalic acid in combination with hexamethylenediamine in an almost equimolar ratio, a2 0 to 40 parts by weight, preferably 20 to 40 parts by weight, particularly preferably 33 parts by weight, of polyamide units AB, which differ from terephthalic acid in combination with hexamethylenediamine in an almost equimolar ratio Derive ratio, the parts by weight of components a1 and a2 together resulting in 100 parts by weight, based on the polyamide units AB.

It is also preferred if the polyamide X consists exclusively of the polyamide units AB and AC. The polyamide X is therefore the system AB/AC, which can also contain monofunctional regulators G as further components. The content of polyamide units AB is preferably 1 to 99 mol%, particularly preferably 10 to 95 mol% and particularly preferably 40 to 90 mol%, and the content of polyamide units AC is preferably 1 to 99 mol%, particularly preferably 5 to 90 mol % and particularly preferably 10 to 60 mol %, based in each case on the sum of the polyamide units AB and AC.

A polyamide X which exclusively comprises the polyamide units AB and AC or exclusively the polyamide units AC is particularly preferred.

Furthermore, particular preference is given to a polyamide X which exclusively comprises the polyamide units AB and AC or exclusively the polyamide units AC, and where the acyclic aliphatic diamines A are selected from 1,6-hexanediamine, 1,10-decanediamine and mixtures thereof, the aromatic dicarboxylic acids B are selected as a mixture of terephthalic acid and isophthalic acid and the phosphorus-containing, aromatic dicarboxylic acids C are selected as 3,5-dicarboxyphenyldiphenylphosphine oxide, 3,5-dicarboxyphenyldimethylphosphine oxide, 3,5-dicarboxyphenyldiethylphosphine oxide and mixtures thereof.

The polyamide X in the form of the precondensates preferably has a solution viscosity nrel, determined using a solution of 0.5 g of polymer granules in 100 ml of m-cresol at 20° C. according to ISO 307:2007, in the range from 1.08 to 1.39, particularly preferably im Range from 1.10 to 1.35, in particular in the range from 1.12 to 1.30.

The polyamide X in high molecular weight or post-condensed form preferably has a solution viscosity nrel, determined using a solution of 0.5 g of polymer granules in 100 ml of m-cresol at 20° C. according to ISO 307:2007, in the range from 1.40 to 2.50, preferably im range from 1.45 to 2.20, in particular in the range from 1.50 to 2.00.

The polyamides X preferably have a phosphorus content of at least 1.0% by weight, particularly preferably a phosphorus content in the range from 1.5 to 7% by weight and particularly preferably in the range from 1.7 to 4.0% by weight.

The inventive polyamides have good flame retardancy and preferably have a V0 flame retardancy classification, determined according to UL94 (“Tests for Flammability of Plastic Materials for Parts in Devices and Applications” by Underwriters Laboratories) on test specimens measuring 127×12.7×0.35 mm, 127 × 12.7 × 0.5 mm, 127 × 12.7 × 0.75 mm, 127 × 12.7 × 1.5 mm and 127 × 12.7 × 3.0 mm, previously conditioned for 48 h in a standard climate at 23 °C and a relative humidity of 50% or the stored in a circulating air oven at 70 °C for a period of 7 days.

The production of polyamide X preferably comprises a polycondensation reaction between at least one phosphorus-containing, aromatic dicarboxylic acid C according to formula 1, 2 and/or 3, where the substituents R1, R2 are each independently C1-C8-alkyl or aryl and the substituents R3 , R4, R5 are each independently H, alkyl, aryl, F, Cl, Br or P(R1)(R2)O, and at least one acyclic aliphatic diamine A and optionally further monomers B, D, E and F, optionally in Presence of monofunctional regulators G and/or process auxiliaries.

Preferred process auxiliaries are inorganic and organic stabilizers, catalysts and defoamers. Preferred catalysts are phosphorus compounds such as phosphoric acid, phosphorous acid, hypophosphorous acid, phenylphosphonic acid, phenylphosphinic acid and/or their salts with monovalent to trivalent cations such as Na, K, Mg, Ca, Zn or Al, and/or their esters , such as B. triphenyl phosphate, triphenyl phosphite or tris (nonylphenyl) phosphite. Hypophosphorous acid and its salts, such as sodium hypophosphite, are particularly preferred as catalysts. In this case, the polyamide X, starting from the monomers A to F in a pressure vessel to form a high molecular weight polymer with a preferred number-average molar mass (Mn) of greater than 3000 g/mol, particularly preferably in the range from 4000 to 20,000 g/mol, or polycondensed to give what is known as a precondensate, which has a lower number-average molar mass (Mn), preferably below 3000 g/mol, particularly preferably in the range from 800 to 2500 g/mol. In subsequent stages, the pre-condensate can be converted into a high-molecular polymer by solid-phase and/or melt post-condensation, with a preferred number-average molar mass (Mn) of greater than 3000 g/mol, particularly preferably greater than 4000 g/mol, in particular in the range of 4000 up to 20,000 g/mol.

The process for the production of polyamide X, which comprises at least the polyamide units AC, is preferably carried out in pressure vessels, after mixing components A and C and optionally other components B, D, E, F, G and optional processing aids as well Water, a pressure phase at 240°C to 330°C with subsequent relaxation at 240°C to 320°C, with subsequent degassing at 240°C to 320°C and discharge of the polyamide in strand form or in powder form, cooling, granulating the strands and drying the granules or powder. Depending on their melting point or glass transition temperature, the precondensates can be post-condensed in the solid phase at temperatures in the range from 150 to 300 °C. The melt post-condensation preferably takes place at temperatures of 300 to 400° C. in an extruder. Mixtures of two or more different precondensates can preferably also be converted into a high molecular weight polyamide by post-condensation. A polyamide X precondensate according to the invention can also be post-condensed together with another precondensate which does not contain the polyamide units AC to give a high molecular weight polyamide X.

Furthermore, the invention also includes the provision of a polyamide molding compound FM containing the polyamide X, and at least one filler and/or at least one additive and/or at least one polyamide Y different from polyamide X.

The polyamide Y is preferably selected from the group consisting of: polyamide 6, polyamide 66, polyamide 610, polyamide 612, polyamide 614, polyamide 616, polyamide 1010, polyamide 1012, polyamide 1014, polyamide 1016, polyamide 11, polyamide 12 , polyamide 6/12, polyamide 61, polyamide 9T, polyamide 10T, polyamide 6T/6I, polyamide 6T/66, polyamide 6T/10T or mixtures thereof. Polyamides 6T/6I, 6T/66, 6T/10T and mixtures thereof are very particularly preferred as polyamide Y.

In a preferred embodiment, the polyamide molding compound FM contains the following components or preferably consists of the following components: 25 to 99.99% by weight of polyamide X 0 to 70% by weight of at least one filler T; 0.01 to 50% by weight of at least one additive S different from X and T; where components S, T and X together add up to 100% by weight.

In a particularly preferred embodiment of the invention, the polyamide molding compound FM contains the following components or preferably consists of the following components: 25 to 100% by weight of a polymer mixture P containing or preferably consisting of 20 to 80% by weight of polyamide X and 20 to 80% by weight polyamide Y, preferably selected from the group consisting of polyamide 6, polyamide 66, polyamide 610, polyamide 612, polyamide 614, polyamide 616, polyamide 1010, polyamide 1012, polyamide 1014, polyamide 1016, polyamide 11 Polyamide 12, Polyamide 6/12, Polyamide 61, Polyamide 9T, Polyamide 10T, Polyamide 6T/6I, Polyamide 6T/66, Polyamide 6T/10T or mixtures thereof, where the sum of X and Y is 100% by weight of the polymer mixture P; 0 to 70% by weight of at least one filler T; 0 to 50% by weight of at least one additive S different from X, Y and T; where the components P, S and T together add up to 100% by weight. The polymer mixture P particularly preferably consists exclusively of components X and Y.

The polyamide Y is a polyamide which is free of polyamide units AC and DC, ie component C does not contain. Polyamide Y preferably contains at least one of the polyamide units AB, AE, DB, DE, F. In a preferred embodiment, the polyamide Y contains only polyamide units AE and/or F, i.e. it is preferably an aliphatic polyamide. It is particularly preferred here if the polyamide Y is selected from the group consisting of polyamide 6, polyamide 66, polyamide 610, polyamide 612, polyamide 614, polyamide 616, polyamide 1010, polyamide 1012, polyamide 1014, polyamide 1016, polyamide 11, polyamide 12, polyamide 6/12 or mixtures thereof.

The polyamide molding compounds FM according to the present invention contain the components X and S or X, T and S or P or P and S or P, T and S or consist preferably exclusively of the components X and S or X, T and S or P or P and S or P, T and S, with the proviso that the components X, T, S or P, T, S add up to 100% by weight. The specified ranges of the quantities for the individual components X, T, S or P, T, S are to be understood in such a way that an arbitrary quantity for each of the individual components can be selected within the specified ranges, provided that the strict requirement is met that the sum of all components X, T, S or P, T, S is 100% by weight.

The phosphorus content of the polymer mixture P is preferably in the range from 0.8 to 6.0% by weight, particularly preferably in the range from 1.2 to 4.5% by weight and particularly preferably in the range from 1.5 to 3.5% by weight.

Component T is a filler which is present in the polyamide molding composition FM at 0 to 70% by weight. The fillers can be present either in fibrous form or in particulate form, individually or as a mixture. Component T can therefore contain fibrous fillers (reinforcing agents) or particulate fillers or else a mixture of reinforcing agents and particulate fillers.

According to a preferred embodiment of the present invention, component T is present in the polyamide molding compound FM at 10 to 60% by weight, more preferably at 20 to 55% by weight and particularly preferably at 25 to 50% by weight , where these quantities relate to the sum of components X, T, S or the sum of components P, T, S or the total weight of the polyamide molding compound FM.

It is particularly preferred if component T consists exclusively of reinforcing agents selected from the group consisting of glass fibers, carbon fibers, boron fibers, aramid fibers, basalt fibers and mixtures thereof. According to a preferred embodiment of the polyamide molding compound according to the invention, component T is formed entirely from glass fibers.

The glass fibers used have a cross-sectional area that is either circular (or synonymously round) or non-circular (or synonymously flat), in which case the dimensional ratio of the major cross-sectional axis to the minor cross-sectional axis is at least 2, preferably im range from 2 to 6.

The reinforcement with glass fibers can be done with short fibers (e.g. chopped glass with a length of 2 to 50 mm) or endless fibers (long glass or rovings). In a preferred embodiment, the glass fibers used according to the invention are short glass fibers with a diameter in the range from 6 to 20 μm and preferably from 9 to 12 μm. The glass fibers are in the form of chopped glass with a length of 2 to 50 mm. In particular, E and/or S glass fibers are used according to the invention. However, all other types of glass fiber, such as e.g. B. A, C, D, M, R glass fibers or any mixtures thereof or mixtures with E and / or S glass fibers can be used. The sizings customary for polyamide, such as e.g. B. various aminosilane sizings are used, with high-temperature-stable sizings being preferred.

In the case of the flat glass fibers, i.e. glass fibers with a non-circular cross-sectional area, those with a dimensional ratio of the main cross-sectional axis to the secondary cross-sectional axis perpendicular thereto of at least 2, preferably from 2.5 to 4.5, in particular from 3 to 4, are preferably used. These so-called flat glass fibers have an oval, elliptical, elliptical (so-called cocoon or cocoon fibre) provided with constriction(s), polygonal, rectangular or almost rectangular cross-sectional area. Another characteristic feature of the flat glass fibers used is that the length of the main cross-sectional axis is preferably in the range from 6 to 40 µm, in particular in the range from 15 to 30 µm, and the length of the secondary cross-sectional axis in the range from 3 to 20 µm, in particular in the range from 4 to 10 µm.

Mixtures of glass fibers with a circular and non-circular cross-section can also be used to reinforce the molding compositions according to the invention, the proportion of flat glass fibers preferably predominating, i.e. making up more than 50% by weight of the total mass of the fibers. The glass fibers can be provided with a size suitable for thermoplastics, in particular for polyamide, containing an adhesion promoter based on an amino or epoxy silane compound.

The flat glass fibers of component T are preferably selected as E-glass fibers according to ASTM D578-00 with a non-circular cross-section, preferably with a composition of 52 to 62% silicon dioxide, 12 to 16% aluminum oxide, 16 to 25% calcium oxide, 0 to 10% borax, 0 to 5% magnesium oxide, 0 to 2% alkali oxides, 0 to 1.5% titanium dioxide and 0 to 0.3% iron oxide. The glass fibers of component T, as flat E-glass fibers, preferably have a density of 2.54 to 2.62 g/cm 3 , a tensile modulus of elasticity of 70 to 75 GPa, a tensile strength of 3000 to 3500 MPa and an elongation at break of 4.5 to 4.8%, whereby the mechanical properties were determined on individual fibers with a diameter of 10 µm and a length of 12.7 mm at 23 °C and a relative humidity of 50%. Component T can also contain particulate fillers, optionally in surface-treated form, selected from the following group: kaolin, calcined kaolin, aluminum oxide, talcum, talc, mica, silicate, quartz, wollastonite, amorphous silicic acids, magnesium carbonate, magnesium hydroxide, chalk, lime , feldspar, solid or hollow glass beads or ground glass, in particular ground glass fibers, and mixtures of elements from this group. Glass microspheres with an average diameter in the range from 5 to 100 μm are particularly preferred as filler, since these tend to give the molded part isotropic properties and thus allow the production of molded parts with low warpage.

According to a preferred embodiment of the present invention, component T consists exclusively of a glass filler selected from the group consisting of glass fibers, ground glass fibers, glass particles, glass flakes, glass spheres, hollow glass spheres or combinations of the aforementioned. If glass spheres or glass particles are selected as component T, their average diameter is from 0.3 to 100 μm, preferably from 0.7 to 30 μm, particularly preferably from 1 to 10 μm.

Another preferred embodiment of the present invention provides that the glass type of component T is selected from the group consisting of E glass, ECR glass, S glass, A glass, AR glass and R glass, in particular E and S glass, as well as mixtures of these types of glass.

According to a preferred embodiment, component T is a high-strength glass fiber or so-called S-glass fiber. This is preferably based on the ternary system silica-alumina-magnesia or on the quaternary system silica-alumina-magnesia-calcia, with a composition of 58 to 70% by weight silica (SiO2), 15 to 30% by weight alumina ( Al2O3), 5 to 15% by weight magnesium oxide (MgO), 0 to 10% by weight calcium oxide (CaO) and 0 to 2% by weight other oxides such as zirconium dioxide (ZrO2), boron oxide (B2O3), titanium dioxide (TiO2), iron oxide (Fe2O3), sodium oxide, potassium oxide or lithium oxide (Li2O) is preferred.

It is particularly preferred if the high-strength glass fiber has the following composition: 62 to 66% by weight silicon dioxide (SiO2), 22 to 27% by weight aluminum oxide (Al2O3), 8 to 12% by weight magnesium oxide ( MgO), 0 to 5% by weight calcium oxide (CaO), 0 to 1% by weight other oxides such as zirconium dioxide (ZrO2), boron oxide (B2O3), titanium dioxide (TiO2), iron oxide (Fe2O3), sodium oxide, potassium oxide and lithium oxide (Li2O).

The high-strength glass fibers (S-glass fibers) preferably have a tensile strength of at least 3700 MPa, preferably at least 3800 or 4000 MPa, and/or an elongation at break of at least 4.8%, preferably at least 4.9 or 5.0% and/or a tensile strength E modulus of more than 75 GPa, preferably more than 78 or 80 GPa, these glass properties being measured on single fibers (pristine single filaments) with a diameter of 10 µm and a length of 12.7 mm at a temperature of 23 °C and a relative humidity of 50% are to be determined.

The inventive polyamide molding composition FM contains 0 to 50% by weight of at least one additive as component S, which is different from component X, T and Y.

According to a preferred embodiment, the inventive polyamide molding compound FM contains 0.01 to 50% by weight or 0.01 to 30% by weight and particularly preferably 0.02 to 20% by weight of at least one additive as component S, these quantities relate to the sum of the components X, T, S or the sum of the components P, T, S or the total weight of the polyamide molding compound FM.

According to a preferred embodiment, component S is selected from the group consisting of lubricants, heat stabilizers, processing stabilizers, processing aids, viscosity modifiers, antioxidants, agents against thermal decomposition and decomposition by ultraviolet light, UV blockers, lubricants and mold release agents, coloring agents, in particular dyes , inorganic pigments, organic pigments, plasticizers, flame retardants, impact modifiers and mixtures thereof.

To improve the flame retardant properties, the polyamide molding compositions FM can also contain flame retardants as additives, the flame retardant additives preferably being halogen-free. Preferred flame retardant additives are phosphinic acid salts and/or diphosphinic acid salts, which are preferably used together with a synergist, in particular a nitrogen-containing synergist and/or a nitrogen- and phosphorus-containing flame retardant, preferably melamine or condensation products of melamine, such as particularly preferably selected from the group: melem, melam, melon , reaction products of melamine with polyphosphoric acid, such as melamine polyphosphate, reaction products of condensation products of melamine with polyphosphoric acid, or mixtures thereof.

In a further embodiment, the synergist is preferably selected as an oxygen-, nitrogen- or sulfur-containing metal compound. Preferred metals are aluminum, calcium, magnesium, barium, sodium, potassium and zinc. Suitable compounds are selected from the group consisting of oxides, hydroxides, carbonates, silicates, borates, phosphates, stannates, alkoxides, carboxylates and combinations or mixtures of these compounds, such as oxide-hydroxydes or oxide-hydroxycarbonates. Examples are magnesium oxide, calcium oxide, aluminum oxide, zinc oxide, barium carbonate, magnesium hydroxide, aluminum hydroxide, boehmite, pseudoboehmite, dihydrotalcite, hydrocalumite, calcium hydroxide, calcium hydroxyapatite, tin oxide hydrate, zinc hydroxide, zinc borate, zinc sulfide, zinc phosphate, sodium carbonate, calcium carbonate, calcium phosphate, magnesium carbonate, basic zinc silicate, zinc stannate . Also possible are systems such as calcium stearate, zinc stearate, magnesium stearate, barium stearate, potassium palmitate, magnesium behenate.

Examples of suitable phosphinic acids for preparing the phosphinic acid salts according to the invention are dimethylphosphinic acid, ethylmethylphosphinic acid, diethylphosphinic acid, methyl-n-propylphosphinic acid, methanedi(methylphosphinic acid), ethane-1,2-di(methylphosphinic acid), and 1,6-hexane -di(methylphosphinic acid), benzene-1,4-di(methylphosphinic acid), methylphenylphosphinic acid, diphenylphosphinic acid. The phosphinic acid salts can be produced, for example, by reacting the phosphinic acid salts in aqueous solution with metal carbonates, metal hydroxides or metal oxides, with essentially monomeric phosphinic acid salts being formed, but depending on the reaction conditions, polymeric phosphinic acid salts may also be formed. The content of these halogen-free flame retardant additives in component S is preferably not more than 10% by weight, particularly preferably not more than 5% by weight, based in each case on the total molding compound FM, and the molding compound FM is particularly preferably free of flame retardant additives.

According to a particularly preferred embodiment, the polyamide molding composition FM contains at least one lubricant as component S, this preferably in a proportion of 0 to 2 wt .-%, particularly preferably from 0.01 to 2.0 wt .-%, particularly preferably from 0.01 to 1.5% by weight and most preferably from 0.02 to 1.0% by weight, based in each case on the total weight of components X, T, S or P, T, S or the molding composition FM. Preference is given here to Al, alkali metal, alkaline earth metal salts, esters or amides of fatty acids having 10 to 44 carbon atoms and preferably having 14 to 44 carbon atoms, the metal ions Na, Mg, Ca and Al being preferred and Ca or Mg being particularly preferred are. Particularly preferred metal salts are Ca stearate and Ca montanate as well as Al stearate. The fatty acids can be monovalent or bivalent. Examples which may be mentioned are pelargonic acid, palmitic acid, lauric acid, margaric acid, dodecanedioic acid, behenic acid and the particularly preferred stearic acid, capric acid and montanic acid (mixture of fatty acids with 30 to 40 carbon atoms).

Furthermore, aliphatic alcohols, which can be 1- to 4-valent, are preferred as lubricants. These alcohols are preferably selected from the group consisting of n-butanol, n-octanol, stearyl alcohol, ethylene glycol, propylene glycol, neopentyl glycol, glycerol, pentaerythritol and mixtures thereof, glycerol and pentaerythritol being preferred.

In addition, aliphatic amines, which can be mono- to tri-valent, are preferred lubricants. Preferred amines are selected from the group consisting of stearylamine, ethylenediamine, propylenediamine, hexamethylenediamine, di(6-aminohexyl)amine and mixtures thereof, with ethylenediamine and hexamethylenediamine being particularly preferred.

Preferred esters or amides of fatty acids are selected from the group consisting of glycerol distearate, glycerol tristearate, ethylenediamine distearate, glycerol monopalmitate, glycerol trilaurate, glycerol monobehenate, pentaerythritol tetrastearate, and mixtures thereof. Furthermore, white oils or silicone oils can also be used as an alternative or in addition.

According to a further preferred embodiment, the polyamide molding composition FM contains at least one heat stabilizer as component S, this preferably in a proportion of 0 to 3% by weight, particularly preferably from 0.02 to 2.0% by weight, based in each case on the total weight of the components X, T, S or P, T, S or the molding compound FM is included.

According to a preferred embodiment, the heat stabilizers are selected from the group consisting of: • Compounds of monovalent or divalent copper, e.g. Salts of monovalent or divalent copper with inorganic or organic acids or monovalent or divalent phenols, the oxides of - Or divalent copper, or the complex compounds of copper salts with ammonia, amines, amides, lactams, cyanides or phosphines, preferably Cu(I) or Cu(II) salts of hydrohalic acids, hydrocyanic acids or the copper salts of aliphatic carboxylic acids. The monovalent copper compounds CuCl, CuBr, CuI, CuCN and Cu2O, and the divalent copper compounds CuCl2, CuSO4, CuO, copper(II) acetate or copper(II) stearate are particularly preferred. The copper compounds are advantageously used in combination with other metal halides, in particular alkali metal halides such as NaI, KI, NaBr, KBr, or ammonium halides, the molar ratio of metal halide to copper halide being 0.5 to 20, preferably 1 to 10 and particularly preferably 3 to 7. • Lanthanide compounds selected from the group consisting of acetates, fluorides, chlorides, bromides, iodides, oxyhalides, sulfates, nitrates, phosphates, chromates, perchlorates, oxalates, the monochalcogenides of sulfur, selenium and tellurium, carbonates, hydroxides, oxides, trifluoromethanesulfonates , acetylacetonates, alcoholates, 2-ethylhexanoates of the lanthanides lanthanum, cerium, praeseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium and - hydrates of the salts mentioned and - mixtures of the said Links. Cerium or lanthanum compounds are particularly preferred, and the use of lanthanum(III) hydroxide, lanthanum(III) oxide hydroxide and cerium tetrahydroxide is particularly preferred here. Furthermore, it is preferred that the cation of the lanthanide compounds has an oxidation number of +III or +IV. The lanthanide compounds are preferably used in combination with alkali metal halides, alkaline earth metal halides and/or the copper compounds mentioned above. • Stabilizers based on secondary aromatic amines, these stabilizers preferably being present in an amount of 0.2 to 2, preferably 0.2 to 1.5% by weight, • Stabilizers based on sterically hindered phenols, these stabilizers preferably being present in an amount of 0.1 to 1.5 , preferably from 0.2 to 1.0% by weight, and • phosphites and phosphonites, and • mixtures of the aforementioned stabilizers.

Particularly preferred examples of stabilizers based on secondary aromatic amines that can be used according to the invention are adducts of phenylenediamine with acetone (Naugard A), adducts of phenylenediamine with linolene, Naugard 445, N,N'-dinaphthyl-p-phenylenediamine, N-phenyl- N'-cyclohexyl-p-phenylenediamine or mixtures of two or more thereof.

In principle, all compounds with a phenolic structure which have at least one bulky group on the phenolic ring are suitable as sterically hindered phenols. Preferred examples of stabilizers based on sterically hindered phenols which can be used according to the invention are N,N'-hexamethylenebis-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide, bis-(3,3-bis- (4'-Hydroxy-3'-tert-butylphenyl)butyric acid) glycol ester, 2,1'-Thioethylbis(3-(3,5-di.tert-butyl-4-hydroxyphenyl)propionate, 4-4 '-butylidene bis (3-methyl-6-tert-butylphenol), triethylene glycol 3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate or mixtures of two or more of these stabilizers.

Preferred phosphites and phosphonites are triphenyl phosphite, diphenylalkyl phosphite, phenyldialkyl phosphite, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylphentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl)phosphite, diisodecylpentaerythritol diphosphite, bis(2,4-di- tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite, bis(2,4 ,6-tris(tert-butylphenyl))pentaerythritol diphosphite, tristearylsorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylenediphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert -butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocin, 6-Fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]- 1,3,2-dioxaphosphocin, bis(2,4-di-tert-butyl-6-methylphenyl)methyl phosphite and bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite. In particular, preferably tris[2-tert-butyl-4-thio(2'-methyl-4'-hydroxy-5'-tert-butyl)phenyl-5-methyl]phenyl phosphite and tris(2,4-di - tert -butylphenyl) phosphite (Irgafos 168).

A preferred embodiment of the heat stabilizer consists in the combination of organic heat stabilizers (in particular Irgafos 168 and Irganox 1010), a bisphenol A based epoxy (in particular Epikote 1001) and a copper stabilization based on Cul and Kl. A commercially available stabilizer mixture consisting made of organic stabilizers and epoxides is, for example, Irgatec NC66 or Recylobyk 4371. Heat stabilization based exclusively on Cul and Kl is particularly preferred mixtures thereof in concentrations of up to 1% by weight, based on the total weight of components X, T, S or P, T, S or the molding composition FM.

Various substituted resorcinols, salicylates, benzotriazoles and benzophenones may be mentioned as UV stabilizers, which are generally used in amounts of up to 2% by weight, based on the weight of the polyamide molding composition FM.

Inorganic pigments such as titanium dioxide, barium sulfate, zinc oxide, ultramarine blue, iron oxide and carbon black and/or graphite, organic pigments such as phthalocyanines, quinacridones, perylenes and dyes such as nigrosine and anthraquinones can also be added as colorants.

Component S can also include impact modifiers, preferably these are selected from the group consisting of polyolefins, polyolefin copolymers, styrene copolymers, styrene block copolymers, ionic ethylene copolymers, which can be partially neutralized by metal ions, and mixtures thereof. The impact modifiers are preferably functionalized. The polyamide molding compositions FM preferably contain 0 to 35% by weight, particularly preferably 5 to 20% by weight, of impact modifiers.

According to a preferred embodiment of the present invention, the impact modifiers of component S are functionalized by copolymerization and/or by grafting. A compound selected from the group consisting of unsaturated carboxylic acids, unsaturated carboxylic acid derivatives and mixtures thereof and/or unsaturated glycidyl compounds is particularly preferably used for this purpose. This is particularly preferably selected from the group consisting of unsaturated carboxylic acid esters, in particular acrylic acid esters and/or methacrylic acid esters, unsaturated carboxylic acid anhydrides, in particular maleic anhydride, glycidylacrylic acid, glycidylmethacrylic acid, α-ethylacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, aconitic acid, tetrahydrophthalic acid, butenylsuccinic acid and mixtures thereof .

If the impact modifiers are functionalized by copolymerization, the proportion by weight of each individual compound used for the functionalization is preferably in the range from 3 to 25% by weight, particularly preferably from 4 to 20% by weight and particularly preferably from 4.5 to 15 % by weight, in each case based on the total weight of the functionalized impact modifiers S.

If the impact modifiers are functionalized by grafting, the proportion by weight of each individual compound used for functionalization is preferably in the range from 0.3 to 2.5% by weight, particularly preferably from 0.4 to 2.0% by weight and particularly preferably from 0.5 to 1.9 % by weight, in each case based on the total weight of the functionalized impact modifiers S.

As impact modifiers are preferably selected polyolefins or polyolefin copolymers from the group consisting of polyethylene, polypropylene, polybutylene, ethylene-α-olefin copolymers, propylene-α-olefin copolymers, ethylene-propylene copolymers, ethylene-propylene Diene copolymers and mixtures thereof, the α-olefins preferably having 3 to 18 carbon atoms. Particularly preferred are the α-olefins selected from the group consisting of propene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene and mixtures thereof. Among the ethylene-α-olefin copolymers, ethylene-propylene copolymers, ethylene-1-butene copolymers or ethylene-propylene-1-butene copolymers are preferred.

The styrene copolymers are preferably styrene copolymers with a comonomer selected from the group consisting of butadiene, isoprene, acrylate and mixtures thereof. The styrene block copolymers are preferably selected from the group consisting of styrene-butadiene-styrene triblock copolymers (SBS), styrene-isoprene-styrene triblock copolymers (SIS), styrene-ethylene/butylene-styrene (SEBS), styrene-ethylene/ propylene styrene triblock copolymer (SEPS) and blends thereof.

The styrene-ethylene/butylene-styrene triblock copolymers are linear triblock copolymers composed of an ethylene/butylene block and two styrene blocks. The styrene-ethylene/propylene-styrene triblock copolymers are linear triblock copolymers composed of an ethylene/propylene block and two styrene blocks.

The styrene content in the styrene-ethylene/butylene-styrene triblock copolymers or styrene-ethylene/propylene-styrene triblock copolymers is preferably from 20 to 45% by weight, more preferably from 25 to 40% by weight and very particularly preferably from 25 to 35% by weight. The ionic ethylene copolymers preferably consist of the monomers selected from the group consisting of ethylene, propylene, butylene, acrylic acid, acrylate, methacrylic acid, methacrylate and mixtures thereof, the acid groups being partially neutralized with metal ions, ethylene-methacrylic acid copolymers being particularly preferred or ethylene-methacrylic acid-acrylate copolymers in which the acid groups are partially neutralized with metal ions. The metal ions used for neutralization are preferably sodium, zinc, potassium, lithium, magnesium ions and mixtures thereof, sodium, zinc and magnesium ions being particularly preferred.

The present invention also includes moldings produced from the polyamides X according to the invention or the polyamide molding compound FM or having at least one region or a coating of a polyamide X or a polyamide molding compound FM, preferably produced by injection molding, injection blow molding, injection compression molding , pultrusion, melt spinning, extrusion or blow molding.

These shaped bodies are preferably selected from the group consisting of fibers, foils, profiles, pipes, containers, semi-finished products, finished parts or hollow bodies, housings, housing parts, frames, protective housings, covers or cladding elements, in particular for electrical devices, electronic devices, electro-optical devices, Electro-optical components, connectors, fans, in particular fan wheels, office automation devices, consumer electronics, components for the automotive sector, in particular selected from cylinder head covers, engine covers, housings for charge air coolers, charge air cooler flaps, intake pipes, intake manifolds, connectors, gear wheels, fan wheels, charge air coolers, headlight housings, reflectors, cornering light adjustment, Gears, plug-in connections, connectors, including those for petrol, diesel, urea and compressed air lines, components for electric vehicles, profiles, foils or layers of multi-layer foils, electronic components, G Housing for electronic components, tools, sockets and fittings for connecting hoses or pipes, electrical or electronic components, a printed circuit board, a part of a printed circuit board, a housing component, a foil, a line, in particular in the form of a switch, a distributor, a relay , a resistor, a capacitor, a coil, a lamp, a diode, an LED, a transistor, a connector, a controller, a memory and/or a sensor.

Finally, the invention also includes the use of a polyamide X according to any one of claims 1 to 8, or a polyamide molding composition FM according to any one of claims 12 to 14, for the production of the moldings described above.

WAYS TO CARRY OUT THE INVENTION

Measurement methods:

Relative viscosity (solution viscosity ηrel)

The relative viscosity was determined at 20° C. in accordance with ISO 307 (2007). For this purpose, 0.5 g of polymer granules were dissolved in 100 ml of m-cresol; the calculation of the relative viscosity (RV) according to RV = t/t0 was based on section 11 of the standard.

Melting point Tm and enthalpy of fusion ΔHm

The melting point and enthalpy of fusion were determined on the granulate according to ISO 11357-3 (2013). The DSC (Differential Scanning Calorimetry) measurements were carried out with a heating rate of 20 K/min.

glass transition temperature Tg

The glass transition temperature Tg was determined according to ISO 11357-2 (2013) on granules by means of differential scanning calorimetry (DSC). After the second heating, the sample was quenched in dry ice. The glass transition temperature (Tg) was determined on the third heating, which was carried out at a heating rate of 20 K/min. The midpoint of the glass transition range, which was given as the glass transition temperature, was determined using the "Half Height" method.

End groups (amino and carboxy end groups)

The amino (NH 2 ) and acid (COOH) end group concentrations are determined using a potentiometric titration. For the amino end groups, 0.2 to 1.0 g of polyamide are dissolved in a mixture of 50 ml of m-cresol and 25 ml of isopropanol at 50 to 90° C. and, after adding aminocaproic acid, titrated with a 0.05 molar perchloric acid solution. To determine the COOH end groups, 0.2 to 1.0 g of the sample to be determined, depending on the solubility, is dissolved in benzyl alcohol or a mixture of o-cresol and benzyl alcohol at 100 °C and, after adding benzoic acid, titrated with a 0.1 molar tetra-n-butylammonium hydroxide solution.

Number average and weight average molar masses (Mn,Mw)

The number and weight-average molar masses of polyamides were determined using gel permeation chromatography (GPC) with universal poly(methyl methacrylate) calibration. GPC analyzes were performed by dissolving 2-4 mg of polyamide granules in 1 mL of hexafluoroisopropanol (HFIP) and passing the solution through an Agilent 1260 Infinity II high-temperature GPC system equipped with a triple detector (refractive index detector, viscometer, and light scattering detector). was equipped. The measurements were carried out using a PL HFIP gel (9 µm particle size) two-column system under the following measurement conditions: column temperature 40 °C, HFIP with 20 mmol sodium trifluoroacetate as solvent, flow rate 1 ml/min, injection volume 100 µl.

Production of the test specimens and UL 94 test (flame retardant classification)

The flammability was tested by vertical burning tests according to UL-94 VB according to IEC 60695-11-10 on specimens measuring 127×12.7×0.5 mm. The specimens were produced using the compression molding process (Lindenberg hot press, 320 - 330 °C). Before the firing tests, the specimens were conditioned for 48 hours in a standard climate at 23°C and a relative humidity of 50% or stored for 7 days at 70°C in a convection oven.

examples

The polyamides PA-1-NK, PA-2-NK and PA-3-NK were polycondensed in two stages. First, the low-molecular precondensates (VK) were prepared from diamine and dicarboxylic acids in the presence of water, which were then converted into the high-molecular polyamides (NC) by solid-phase and melt post-condensation, either alone or mixed with another precondensate.

Examples PA-1-VK to PA-3-VK

In a 200 ml autoclave, the diamines (component A) and dicarboxylic acids (components B, C, E) were filled together with 15 percent by weight of water, based on the total batch, with the individual amounts being selected according to the composition given in Table 1 were that the total amount was about 100 g. The batch was heated to a temperature of 260° C. and then held at this temperature for 2.5 hours during the printing phase. The low molecular weight polycondensate formed was then discharged from the autoclave via an opening with steam. The pre-condensate was dried at 110° C. and a vacuum of 30 mbar for 24 hours before it was subjected to post-polycondensation.

Examples PA-1-NK to PA-3-NK

In the examples PA-1-NK and PA-2-NK the respective pre-condensate was used alone (PA-1-VK, PA-2-VK) and in the example PA-3-NK a mixture of two polyamide Pre-condensates (PA-1-VK and PA-3-VK in a weight ratio of 1:1) are post-condensed in two stages as described below.

In a first stage, the pre-condensates were post-condensed over a period of 24 to 120 hours in a Binder VDL53 vacuum oven at 200° C. and 30 mbar in the solid phase before they were then in a second stage in a microcompounder (Xplore MC 15HT). were further polycondensed at 300 to 330 °C. The microextruder is equipped with two valves and a heated channel that allows material to be recycled into the top of the microextruder. Despite the short length of the screw, residence times of several minutes can be achieved thanks to this closed-loop operation. The average residence time in the examples was 5 minutes, the screw speed was 50 rpm, the screw torque was 40 Nm, the temperature of the barrel was 330°C, the temperature of the extruded melt was 322°C. The polyamides were emptied into a metal pan and cooled to ambient temperature under an air atmosphere. The polymer sample was then granulated (Hellweg M50/80) and the granules dried for 24 hours at 110° C. under reduced pressure (30 mbar).

Table 1. Composition and properties of the pre- and post-condensates

1,6-hexanediamine (component A) mol% 100 100 100 terephthalic acid (component B) mol% - 55 3,5-dicarboxyphenyldiphenylphosphine oxide (component C) mol% 60 100 - adipic acid (component E) mol-% 40 45 Properties Relative viscosity (ηrel) - 1.17 1.18 1.15 amine end groups (NH2) µeq./g 300 275 1900 acid end groups (COOH) µeq./g 350 285 1800 post-condensates PA-1-NK PA-2 -NK PA-3-N K Educts for post-condensation (weight ratio) PA-1-VK (100%) PA-2-VK (100%) PA-1-VK and PA-3-VK (1:1) Relative viscosity (ηrel) - 1.70 1.78 1.85 Number average molar mass Mn g/mol 7840 9250 13700 Weight average molar mass Mw g/mol 22480 25440 37700 Polydispersity Mw/Mn - 2.9 2.8 2.8 Glass transition temperature °C 125 140 95 Melting point °C - - ΔHm J. Heat of fusion /g - - 25 Phosphorus content wt % 5.2 6.9 2.6 Fire classification UL94 Sample thickness 0 5 mm Conditioning 48 h, 23 °C, 50% RH - V0 V0 V0 * Values of the 2nd heating, * Values of the 3rd heating

Claims (15)

1. Polyamide X with the polyamide units AB/AC/AE/DB/DC/DE/F, where at least the polyamide units AC must be present, the polyamide units AB, AE, DB, DC, DE and F are optional and where the monomer Units A, B, C, D, E and F are derived from the following molecules, which are amidically bound in the polyamide X: A: Acyclic aliphatic diamines; B: Phosphorus-free aromatic dicarboxylic acids; C: Phosphorus-containing, aromatic dicarboxylic acids according to formula 1, 2 and/or 3, where the substituents R1, R2 are each independently C1 - C8-alkyl or aryl and the substituents R3, R4, R5 are each independently H, alkyl, aryl, F, are Cl, Br or P(R1)(R2)O; D: Cycloaliphatic diamines or diamines with aromatic structural units; E: Aliphatic dicarboxylic acids F: α,ω-aminocarboxylic acids, lactams. 2. Polyamide according to claim 1, characterized in that the content of the polyamide units AC or the sum of the contents of the polyamide units AC and DC is 1 to 100 mol%, preferably 5 to 80 mol% and particularly preferably 10 to 60 mol%, in each case based on a polyamide X with the polyamide units AB/AC/AE/DB/DC/DE/F. 3. Polyamide according to one of the preceding claims, characterized in that at least one of the selection groups mentioned below for components A to F is selected, preferably the selection groups for components A and C are selected, particularly preferably the selection groups for components A, B and C are selected and particularly preferably all selection groups are selected at the same time: A: The acyclic aliphatic diamines are selected from the group consisting of 1,6-hexanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,12-dodecanediamine, preferably selected as 1,6-hexanediamine or 1,10 -decanediamine; B: the aromatic dicarboxylic acids are selected from the group consisting of terephthalic acid, isophthalic acid and mixtures thereof, preferably selected as a mixture of terephthalic acid and isophthalic acid; C: the phosphorus-containing, aromatic dicarboxylic acids are selected from the group consisting of 3,5-dicarboxyphenyldiphenylphosphine oxide, 3,5-dicarboxyphenyldimethylphosphine oxide, 3,5-dicarboxyphenyldiethylphosphine oxide, 2,4-dicarboxyphenyldiphenylphosphine oxide, 2,4-dicarboxyphenyldimethylphosphine oxide, 2, 4-dicarboxyphenyldiethylphosphine oxide, preferably selected from 3,5-dicarboxyphenyldiphenylphosphine oxide, 3,5-dicarboxyphenyldimethylphosphine oxide or 3,5-dicarboxyphenyldiethylphosphine oxide, particularly preferably selected from 3,5-dicarboxyphenyldiphenylphosphine oxide; D: the cycloaliphatic diamines and the diamines with aromatic structural units are selected from the group consisting of bis(4-amino-3-methylcyclohexyl)methane, bis(4-aminocyclohexyl)methane, bis(4-amino-3,5- dimethylcyclohexyl)methane, m-xylylenediamine, p-xylylenediamine, and mixtures thereof; E: the aliphatic dicarboxylic acids are selected from the group consisting of adipic acid, 1,10-decanedioic acid, 1,12-dodecanedioic acid, 1,14-tetradecanedioic acid, 1,16-hexadecanedioic acid, cyclohexane-1,3-dicarboxylic acid, cyclohexane-1, 4-dicarboxylic acid and mixtures thereof;. F: the α,ω-aminocarboxylic acids or the lactams F are selected from the group consisting of α,ω-aminoundecanoic acid, caprolactam and laurolactam and mixtures thereof. 4. Polyamide according to one of the preceding claims, characterized in that the polyamide X comprises at least the polyamide units AB and AC; or consists exclusively of the polyamide units AB and AC; or preferably consists exclusively of the polyamide units AC. 5. Polyamide according to one of the preceding claims, characterized in that the polyamide units AB are selected from the group consisting of the polyamide units 6I, 6T, 81, 8T, 91, 9T, 101, 10T, 121, 12T, 6I/6, 6T /6, 9I/6, 9T/6, 10I/6, 10T/6, 12I/6, 12T/6, 6I/12, 6T/12, 9I/12, 9T/12, 10I/12, 10T/12 , 12I/12, 12T/12, 6I/6T, 9I/9T, 10I/10T, 12I/12T; or the polyamide units AB are composed as follows: a1 50 to 100 parts by weight, preferably 55 to 85 parts by weight, particularly preferably 60 to 80 parts by weight, of polyamide units AB which are derived from isophthalic acid in combination with hexamethylenediamine in an almost equimolar ratio, a2 0 to 50 parts by weight, preferably 15 to 45 parts by weight, particularly preferably 20 to 40 parts by weight, of polyamide units AB which are derived from terephthalic acid in combination with hexamethylenediamine in an almost equimolar ratio, and wherein the parts by weight of components a1 and a2 add up to 100 parts by weight. 6. Polyamide according to one of the preceding claims, characterized in that the content of the polyamide units AB 1 to 99 mol%, preferably 10 to 95 mol%, particularly preferably 40 to 90 mol% and the content of the polyamide units AC 1 to 99 mol %, preferably 5 to 90 mol %, particularly preferably 10 to 60 mol %, based in each case on the sum of the polyamide units AB and AC. 7. Polyamide according to one of the preceding claims, characterized in that the polyamide X in the form of the precondensates has a solution viscosity ηrel, determined using a solution of 0.5 g of polymer granules in 100 ml of m-cresol at 20° C. according to ISO 307:2007, in the range from 1.08 to 1.39, particularly preferably in the range from 1.10 to 1.35 , in particular in the range from 1.12 to 1.30; and or the polyamide X in high molecular weight or post-condensed form has a solution viscosity nrel, determined using a solution of 0.5 g of polymer granules in 100 ml of m-cresol at 20° C. according to ISO 307:2007, in the range from 1.40 to 2.50, preferably in the range from 1.45 to 2.20 , in particular in the range from 1.50 to 2.00. 8. Polyamide according to one of the preceding claims, characterized in that the polyamide X has a flame retardant classification V0, determined according to UL94 on test specimens with the dimensions 127 × 12.7 × 0.35 mm, 127 × 12.7 × 0.5 mm, 127 × 12.7 × 0.75 mm, 127 × 12.7 × 1.5 mm and 127 × 12.7 × 3.0 mm, which were previously conditioned for 48 hours in a standard climate at 23 °C and a relative humidity of 50% or stored for 7 days at 70 °C in a convection oven. 9. A process for preparing a polyamide according to any one of claims 1 to 8, characterized in that the process involves a polycondensation reaction between at least one phosphorus-containing, aromatic dicarboxylic acid C of the formula 1, 2 and/or 3, where the substituents R1, R2 are each independently of the other C1 - C8 alkyl or aryl and the substituents R3, R4, R5 are each independently H, alkyl, aryl, F, Cl, Br or P(R1)(R2)O; and at least one acyclic aliphatic diamine A; and optionally further monomers B, D, E and F, optionally in the presence of monofunctional regulators G and/or process auxiliaries. 10. Polyamide molding composition FM containing the polyamide X according to any one of claims 1 to 8, and at least one filler and/or at least one additive and/or at least one polyamide Y different from polyamide X. 11. Polyamide molding composition FM according to claim 10, characterized in that it contains the following components or preferably consists of the following components: 25 to 99.99% by weight of polyamide X 0 to 70% by weight of at least one filler T; 0.01 to 50% by weight of at least one additive S different from X and T; where components S, T and X together add up to 100% by weight. 12. Polyamide molding compound FM according to claim 10, characterized in that the polyamide molding compound FM contains the following components or preferably consists of the following components: 25 to 100% by weight of a polymer mixture P containing or preferably consisting of 20 to 80% by weight of polyamide X and 20 to 80% by weight of polyamide Y, preferably selected from the group consisting of polyamide 6, polyamide 66, polyamide 610 , Polyamide 612, Polyamide 614, Polyamide 616, Polyamide 11, Polyamide 12, Polyamide 6/12 or mixtures thereof, where the sum of X and Y is 100% by weight of the polymer mixture P; 0 to 70% by weight of at least one filler T; 0 to 50% by weight of at least one additive S different from X, Y and T; where the components P, S and T together add up to 100% by weight. 13. Shaped body made from a polyamide X according to any one of claims 1 to 8, or from a polyamide molding composition FM according to any one of claims 10 to 12 or having at least one region or a coating made from a polyamide X according to any one of claims 1 to 8, or from a polyamide molding composition according to any one of claims 10 to 12, preferably produced by injection molding, injection blow molding, injection compression molding, pultrusion, melt spinning, extrusion or blow molding. 14. Shaped body according to claim 13, characterized in that the shaped body is selected from the group consisting of fibers, foils, profiles, pipes, containers, semi-finished products, finished parts or hollow bodies, housings, housing parts, frames, protective housings, covers or cladding elements, in particular for Electrical devices, electronic devices, electro-optical devices, electro-optical components, connectors, fans, in particular fan wheels, office automation devices, consumer electronics, components for the automotive sector, in particular selected from cylinder head covers, engine covers, housings for charge air coolers, charge air cooler flaps, intake pipes, intake manifolds, connectors, gear wheels, fan wheels, charge air coolers , headlight housings, reflectors, cornering light adjustment, gears, plug-in connections, connectors, including those for petrol, diesel, urea and compressed air lines, components for electric vehicles, profiles, foils or layers of more Layer foils, electronic components, housings for electronic components, tools, nozzles and fittings for connecting hoses or pipes, electrical or electronic components, a printed circuit board, part of a printed circuit board, a housing component, a film, a line, in particular in the form of a switch, a distributor, a relay, a resistor, a capacitor, a coil, a lamp, a diode, an LED, a transistor, a connector, a controller, a memory and/or a sensor. 15. Use of a polyamide X according to any one of claims 1 to 8, or of a polyamide molding compound FM according to any one of claims 10 to 12, for the production of shaped bodies according to claims 13 and 14, in particular fibers, foils, profiles, pipes, Containers, semi-finished products, finished parts or hollow bodies and for coating molded bodies.