WO2014198756A1

WO2014198756A1 - Semi-aromatic copolyamides based on terephthalic acid and aliphatic diamines

Info

Publication number: WO2014198756A1
Application number: PCT/EP2014/062102
Authority: WO
Inventors: Christian Schmidt; Florian Richter; Joachim Clauss; Axel Wilms; Gad Kory; Arnold Schneller; Achim Stammer; Volker Rauschenberger; Stefan Schwiegk
Original assignee: Basf Se
Priority date: 2013-06-12
Filing date: 2014-06-11
Publication date: 2014-12-18

Abstract

The invention relates to semi-aromatic copolyamides which are based on terephthalic acid and aliphatic diamines and which contain repeating units that are derived from terephthalic acid and aliphatic diamines and have improved processing properties as compared to conventional copolyamides based on terephthalic acid and aliphatic diamines.

Description

Partially aromatic copolyamides based on terephthalic acid and aliphatic diamines

description

The invention relates to partially aromatic copolyamides based on terephthalic acid and aliphatic diamines which have repeating units which are derived from terephthalic acid and aliphatic diamines and which have better processing properties compared to conventional copolyamides based on terephthalic acid and aliphatic diamines.

Partaromatic copolyamides based on terephthalic acid and aliphatic diamines, in particular those with high terephthalic acid content, are semicrystalline, thermoplastic polymers and are of great interest as modern materials. They are characterized in particular by their high temperature resistance and thus belong to the group of high-temperature polyamides (HTPA).

An important field of application of HTPA is the production of electrical and electronic components, in particular polymers based on polyphthalamide (PPA) are suitable for use in soldering processes under lead-free conditions (lead free soldering). Among other things, HTPAs are used to manufacture connectors, microswitches and buttons and semiconductor components, such as reflector housings of light-emitting diodes (LEDs). Another important field of application of HTPA are automotive applications in the high temperature range. Here, it is particularly important to have good heat aging resistance, high strength and toughness and weld strength of the polymers used. Amorphous HTPA or those with very low crystalline proportions are transparent and are particularly suitable for applications in which transparency is advantageous. Semi-crystalline HTPA are generally characterized by improved chemical resistance, a durable resistance at high ambient temperature and are suitable for. For applications in the engine compartment area.

Polyamides for use in molding compositions for high-temperature applications must have a complex property profile, with good mechanical properties having to be reconciled with good processability even in the case of long-term thermal loading. For example, although high levels of hexamethylene diamine / terephthalic acid improve crystallinity and significantly increase glass transition temperatures, processability often deteriorates with increasing content of these monomer units due to high melting temperatures. Pure polyamide 6.T, ie hexamethylenediamine (HMD) and terephthalic acid acid (T) built polyamide can not be processed without thermal degradation from the melt, since the melting point is above the decomposition temperature of the polymer (T _m »340 ° C). By using additional comonomers (diamines or diacids), the melting point of the polyamide can be lowered. However, the comonomers generally disturb the crystalline order and not only lower the melting point, but also reduce the crystallinity in the polymer and thus worsen its mechanical properties, especially at higher temperatures. In addition, the crystallization is often kinetically inhibited or proceeds only comparatively slowly. This has the consequence, for example, that the injection molding cycle times are increased because the polymer requires a longer time for solidification. However, the lower crystallinity also adversely affects other properties of the polymer, such as water absorption and chemical resistance or the mechanical properties above the glass transition temperature.

EP 310 752 A2 describes crystalline copolyamides based on terephthalic acid, isophthalic acid and hexamethylenediamine, in which the molar ratio of terephthalic acid to isophthalic acid is in the range from 81:19 to 99: 1. However, the copolyamides show a delayed crystallization behavior.

EP 394 029 describes polyamide molding compositions based on copolyamides which have repeating units of terephthalamide units, isophthalamide units and adipamide units and which are to have improved heat resistance.

EP 667 367 A2 describes partially aromatic, partially crystalline thermoplastic copolyamides based on terephthalic acid and hexamethylenediamine which have repeating units which are derived from isophthalamides and contain small amounts of condensed cyclic diamines.

However, the solidification behavior and / or the crystallinity of the aforementioned copolyamides are unsatisfactory.

One way to accelerate the solidification of HTPAs is to use nucleating agents. Nucleating agents for polyamides usually consist of inorganic particles, organic salts and polymeric nucleating agents. However, the use of such nucleating agents is not always possible and also associated with additional costs. EP 395 414 describes HTPA compounds containing a thermotropic liquid crystalline polymer capable of nucleating in HTPA melts. The HTPA compounds described there have higher crystallization rates than the pure HTPAs. However, the liquid-crystalline polymers are comparatively expensive.

There is still a need for partially aromatic copolyamides for polyamide molding compositions which have an improved property profile with regard to their processability, in particular their solidification behavior and the resulting mechanical properties at high temperatures, in particular high crystallinity. In particular, this should be achieved without or with less use of additives.

The present invention is based on the object to provide partially aromatic copolyamides having improved properties. These are said to be especially suitable for the production of polyamide molding compounds from which components for the automotive industry and the electrical / electronics sector are preferably produced.

It has surprisingly been found that partially aromatic copolyamides based on terephthalic acid and aliphatic diamines which have at least 55 mol% of repeat units derived from terephthalic acid amides, ie partly aromatic copolyamides having a terephthalic acid content of at least 55 mol%, based on the acid component, and a melting enthalpy of at least 55 J / g, in particular at least 60 J / g, which simultaneously have the smallest possible difference in the melting temperature T _m (2) and the crystallization temperature T _k , ie the difference T _m (2) - T _k is not more than 40 K, in particular not more than 35 K, possess advantageous processing properties, in particular faster solidification, and at the same time have good mechanical properties even at elevated temperature. It is assumed that, despite the high enthalpy of fusion, which is characteristic for high crystallinity and ensures high mechanical strengths, due to the small difference T _m (2) - T k a particularly favorable solidification behavior, ie rapid solidification, can be achieved. These properties can be surprisingly changed by selecting suitable comonomers in the desired manner.

Accordingly, the present invention relates to partially aromatic copolyamides based on terephthalic acid and aliphatic diamines which have at least 55 mol% of repeat units which are derived from terephthalic acid amides having a melting enthalpy ΔΗ (2) of at least 55 J / g, in particular at least 60 J / g and a difference T _m (2) - T _k of not more than 40 K, in particular not more than 35 K, where T _m (2) is the melting temperature in Kelvin and T _{k is} the crystallization temperature in Kelvin means. Melt enthalpy ΔΗ (2), crystallization temperature T _k and melting temperature T _m (2) are determined by differential scanning calorimetry (DSC) in a manner known per se (DIN EN ISO 1 1357, parts 1 and 3). The DSC measurement is carried out on thermally conditioned samples. For this purpose, it is expedient to repeat the DSC measurement on one and the same sample once or twice. After the first heating, the sample is kept in the melt for 5 minutes in order to extinguish the thermal history of the copolyamide and thus to ensure a defined thermal history of the respective copolyamide (thermally conditioned copolyamide). The index (2) at enthalpy of fusion ΔΗ (2) and melting temperature T _m (2) means that the evaluation is made on the basis of the second heating curve (1st repetition).

The determination of the enthalpy of fusion ΔΗ (2), crystallization temperature Tk and

Melting temperature T _m (2) is carried out under nitrogen in open aluminum crucibles at a

Heating rate and cooling rate of 20 K / min. Measurement and evaluation are carried out according to DIN EN ISO 1 1357-3.

The melting temperature T _m (2) is the endothermic peak maximum of the DSC curve during the second heating according to a defined thermal history (see above). To determine the enthalpy of melting ΔΗ (2), a baseline is applied to the endothermic melting peak by connecting the peak initial temperature to the peak end temperature. The enthalpy of melting ΔΗ (2) is obtained by determining the area between the baseline and the endothermic melting peak. The crystallization temperature T _k is the exothermic peak minimum of the DSC curve on first cooling at 20 K / min according to a defined thermal history.

Another object of the invention are polyamide molding compositions containing a partially aromatic copolyamide, as defined above and below.

Another object of the invention is the use of a partially aromatic co-polyamide for the production of polyamide molding compositions, which are used in particular for the production of components for automotive applications in the high temperature range and the electrical / electronics sector.

The invention also provides a process for the identification of partly aromatic copolyamides PA based on terephthalic acid and aliphatic diamines, which have at least 55 mol% of repeat units derived from terephthalic acid amides which have good elevated temperature mechanical properties and improved processability, especially in thermoplastic molding processes, characterized the crystallization temperature Tk and the melting temperature T _m (2) determined by DSC on a thermally conditioned sample of the copolyamide PA and a copolyamide selected which has a enthalpy of fusion ΔΗ (2) of at least 55 J / g and in particular at least 60 J / g and at the difference T _m (2) - T _{k is} not more than 40 K, in particular not more than 35 K.

The partly aromatic copolyamides PA according to the invention based on terephthalic acid and aliphatic diamines are typically obtained by co-condensation of an acid component S, which is at least 55 mol%, based on all monomers of the acid component, terephthalic acid (hereinafter component a)) and optionally one or more others Dicarboxylic acids or amide-forming derivatives thereof, comprising a diamine component D comprising at least one aliphatic diamine and optionally comprising one or more further diamines, wherein the proportion of aliphatic diamines is generally at least 55 mol%, based on the total amount of amines in the Amine component comprises, obtained. In the preparation, a lactam component L may also be present. The monomers of the acid and the diamine component and optionally used lactam component form by the condensation repeat units or end groups in the form of amides derived from the respective monomers. These usually make up 95 mol%, in particular 99 mol%, of all repeat units and end groups present in the copolyamide. In addition, the copolyamide may also have small amounts of other repeating units, which may result from degradation or side reactions of the monomers, for example the diamines.

The molar ratio of the acid component S to the amine component D is preferably in the range of 0.9: 1 to 1, 1: 1 and in particular in the range of 0.99: 1 to 1: 1, 05 and especially in the range of 1, 01: 1 to 1, 05: 1.

For the purposes of the invention, aliphatic diamines are understood as meaning compounds which have two primary amino groups which are bonded to a linear or branched, non-cyclic hydrocarbon radical, the hydrocarbon radical preferably being saturated and preferably having from 4 to 18 carbon atoms. Preferred aliphatic diamines are those of the formula H 2 N-A'-NH 2, where A is linear or branched alkanediyl having 5 to 18 C atoms and in particular 6 to 16 C atoms. Preferred aliphatic diamines are in particular 2-methyl-1, 5-diamino pentane (Α 'is 2-methylpentane-1, 5-diyl), hexamethylenediamine (A' is 1,6-hexanediyl) and diamines of the formula H2N-A-NH2, where A is linear or branched alkanediyl of 8 to 16 C atoms and in particular 10 to 14 carbon atoms and mixtures thereof.

Preferred embodiments of inventive copolyamides generally contain at least one monomer in a condensed form, which is selected from

Diamines of the formula H2N-A-NH2, wherein A is linear or branched alkanediyl having 8 to 16 carbon atoms and in particular 10 to 14 carbon atoms; and

- Dicarboxylic acids of the formula HOOC-B-COOH (hereinafter component c)), wherein B is an aliphatic or alicyclic hydrocarbon radical having 6 to 14 carbon atoms and in particular linear or branched C6-C14 alkanediyl means. Examples of diamines of the formula H2N-A-NH2 are 1, 8-diaminooctane (A = 1, 8-octanediyl), 1, 9-diaminononane (A = 1, 9-nonanediyl), 1, 10-diaminodecane (A = 1, 10-decanediyl), 1,1,1-diaminoundecane (A = 1,1,1-undecanediyl) and 1,12-diaminododecane (A = 1,12-dodecanediyl). Preferably, the diamines of the formula H2N-A-NH2 are selected from 1, 10-diaminodecane and 1, 12-diaminododecane and mixtures thereof. The proportion of the diamines of the formula H2N-A-NH2 can in principle be up to 100 mol%, in which case the copolyamide PA then comprises at least one further comonomer which is different from terephthalic acid and the diamines of the formula H2N-A-NH2 , In certain embodiments of the invention, the diamine of the formula H2N-A-NH2 will not exceed 45 mol%, in particular 40 mol%, based on the constituents of the diamine component D and, if present, is in the range from 2 to 45 mol In other embodiments, the copolyamide PA contains at least one diamine of the formula H2N-A-NH2 in an amount in the range from 40 to 100 mol%. %, in particular in the range of 45 to 99 mol% or in the range of 60 to 99 mol%, based on the constituents of the diamine component D. In further embodiments, the copolyamide PA contains no diamine of the formula H2N-A-NH2 condensed or not more than 5 mol% or not more than 2 mol% based on the components of the diamine component D.

Examples of dicarboxylic acids of the formula HOOC-B-COOH are 1,8-octanedioic acid (B = 1,6-hexanediyl), 1,1,10-decanedioic acid (sebacic acid, B = 1,8-octanediyl), 1,12-dodecanedioic acid (B = 1, 10-decanediyl) and 1, 14-tetradecanedioic acid (B = 1, 12-dodecanediyl). The dicarboxylic acid of the formula particularly preferably comprises the formula HOOC-B-COOH

1, 12-dodecanedioic acid or consists of 1, 12-dodecanedioic acid. Also special Preferably, the dicarboxylic acid of the formula HOOC-B-COOH comprises 1, 10-decanedioic acid or consists of 1, 10-decanedioic acid. Naturally, the proportion of the dicarboxylic acid of the formula HOOC-B-COOH will not exceed 45 mol%, in particular 40 mol%, based on the constituents of the acid components S and, in certain embodiments, in the range from 2 to 45 mol%, in particular in the range of 5 to 40 mol%, based on the constituents of the acid components S. In other embodiments, the copolyamide contains no dicarboxylic acids of the formula

HOOC-B-COOH condensed or not more than 5 mol% or not more than 2 mol%, based on the components of the acid component S.

Besides terephthalic acid and the aliphatic diamines, the copolyamides according to the invention thereof may contain various comonomers in a condensed form. Examples of suitable comonomers are:

Isophthalic.

- Diamines of the formula H2N-Q-NH2, wherein Q is a saturated alicyclic or araliphatic hydrocarbon radical having 8 to 18 carbon atoms (hereinafter component e)). Alicyclic radicals are, for example, those which contain one or two cyclohexanediyl radicals and optionally one or two C 1 -C 3 -alkanediyl groups, eg. Methylene groups, wherein the cyclohexanyl radicals are unsubstituted or have 1, 2, 3 or 4 methyl groups. Araliphatic hydrocarbon radicals are those which have at least one aromatic divalent radical, for example a phenylene radical and at least one alkanediyl group having preferably 1 to 3 C atoms. Examples of such diamines are isophoronediamine (IPDA; 3-aminomethyl-3,5,5-trimethylcyclohexylamine), bis-

(3-methyl-4-aminocyclohexyl) methane (MACM), 4,4 '- (aminocyclohexyl) methane (PACM), m-xylylenediamine and p-xylylenediamine. The diamine of the formula H2N-Q-NH2 particularly preferably comprises isophoronediamine or consists of isophoronediamine.

Saturated, monocyclic lactams having 6 to 16 C atoms, in particular 8 to 14 C atoms (hereinafter component f)), for. B. caprolactam, in particular ε-caprolactam, capryllactam, enanthlactam, laurolactam and mixtures thereof. The monocyclic lactam particularly preferably comprises or consists of at least one lactam from the group valerolactam, caprolactam or laurolactam. In particular, the monocyclic lactam comprises laurolactam or consists of laurolactam.

The proportion of isophthalic acid usually makes up not more than 45 mol%, in particular not more than 30 mol% and especially 25 mol%, based on the total amount of all constituents of the acid component. In a preferred embodiment of Invention comprises the acid component not more than 10 mol%, in particular not more than 5 mol% of isophthalic acid, based on the total amount of all components of the acid component S. The proportion of diamines of the formula H2N-Q-NH2 usually makes no more than

45 mol%, in particular not more than 30 mol%, based on the total amount of all components of the diamine components. In preferred embodiments of the invention, the diamine component D comprises, for example, 1 to 40 mol% and in particular 2 to 30 mol%, based on the total amount of all constituents of the diamine component D. In another embodiment of the invention, the diamine component comprises no or no longer as 5 mol% of diamines of the formula H2N-Q-NH2, based on the total amount of all components of the acid component S.

In preferred copolyamides PA, the diamine component comprises at least one diamine of the formula H2N-A-NH2, preferably in the amounts indicated above, and hexamethylenediamine or the diamine component consists thereof.

In likewise preferred copolyamides PA, the diamine component comprises at least one diamine of the formula H 2 N-A-NH 2, preferably in the amounts indicated above, and one or more further alicyclic or araliphatic diamines of the formula H 2 N-Q-NH 2 as defined above, preferably in the above specified amounts, in particular isophorone diamine, or it consists thereof.

In likewise preferred copolyamides PA, the diamine component comprises at least one diamine of the formula H 2 N-A-NH 2, preferably in the abovementioned

Amounts, hexamethylenediamine and optionally one or more further alicyclic or araliphatic diamines of the formula H2N-Q-NH2 as defined above, preferably in the amounts indicated above, in particular isophoronediamine, or it consists thereof.

The partially aromatic copolyamides PA according to the invention are preferably selected from copolyamides PA1, PA2, PA3 and PA4 which are defined in more detail below.

Copolyamides PA1 contain in condensed form or consist of the following acid, diamine and lactam components:

as acid component S:

(a) 55 to 100 mol% or 55 to 98 mol% or 60 to 95 mol% terephthalic acid, (b1) 0 to 45 mol%, in particular 0 to 10 mol% isophthalic acid,

(b2) 0 to 45 mol%, e.g. B. 2 to 45 mol%, in particular 5 to 40 mol% of one or more dicarboxylic acids of the formula HO 2 C-B-CO 2 H as defined above, in particular at least one dicarboxylic acid which is selected from 1, 10-decanedioic acid, 1, 12 Dodecanedioic acid and 1,1,4-tetradecanedioic acid;

as the diamine component D:

(d) 55 to 100 mol% or 55 to 98 mol% or 60 to 95 mol% hexamethylendiamine,

(c2) 0 to 45 mol%, e.g. B. 2 to 45 mol%, in particular 5 to 40 mol% of one or more diamines of the formula H2N-A-NH2, as defined above, in particular at least one diamine of the formula H2N-A-NH2, which is selected from 1, 10-diaminodecane and 1, 12-diaminododecane; and optionally as Lactamkomponente L:

(e) 0 to 10 mol% of one or more saturated, monocyclic lactams having 6 to 16 carbon atoms as defined above, which is preferably selected from valerolactam, caprolactam and laurolactam and which in particular comprises laurolactam or consists of laurolactam; in each case the components a), b1) and b2) and c1) and c2) together give 100 mol%, the component e) is based on the number of moles of the amine component D and wherein the copolyamide PA1 at least one of the components b2) and c2 ) in an amount of at least 2 mol%, in particular at least 5 mol% z. B. 2 to 45 mol% or 5 to 40 mol%, condensed. A preferred group of polyamides PA1 is in a condensed form or consists of the following acid and diamine components:

as acid component S:

(a) 55 to 98 mole%, especially 60 to 95 mole% terephthalic acid,

(b1) 0 to 10 mol% isophthalic acid,

(b2) 2 to 45 mol%, in particular 5 to 40 mol% of one or more dicarboxylic acids of the formula HO 2 C-B-CO 2 H, as defined above, in particular at least one dicarboxylic acid selected from 1, 10-decanedioic acid, 1, 12-dodecanedioic acid and 1, 14-tetradecanedioic acid;

as the diamine component D:

(d) 90 to 100 mole% or 95 to 100 mole% hexamethylenediamine,

(c2) 0 to 10 mol%, in particular 0 to 5 mol% of one or more diamines of the formula H2N-A-NH2, as defined above, in particular at least one diamine of the formula H2N-A-NH2, which is selected from 1 , 10-diamino-decane and 1, 12-diaminododecane; wherein in each case the components a), b1) and b2) and c1) and c2) together give 100 mol%.

A likewise preferred group of polyamides PA1 contains in a condensed form or consists of the following acid and diamine components:

as acid component S:

(a) 90 to 100 mol%, in particular 95 to 100 mol% terephthalic acid, (b1) 0 to 10 mol% isophthalic acid,

(b2) 0 to 10 mol%, in particular 0 to 5 mol%, of one or more dicarboxylic acids of the formula HO 2 C-B-CO 2 H, as defined above, in particular at least one dicarboxylic acid selected from 1, 10-decane diacid, 1, 12-dodecanedioic acid and 1, 14-tetradecanedioic acid;

as the diamine component D:

(c1) 55 to 98 mol% in particular 60 to 95 mol% hexamethylenediamine, (c2) 2 to 45 mol%, in particular 5 to 40 mol% of one or more diamines of the formula H2N-A-NH2, as defined above , in particular at least one diamine of the formula H2N-A-NH2 which is selected from 1, 10-diamino-decane and 1, 12-diaminododecane;

wherein in each case the components a), b1) and b2) and c1) and c2) together give 100 mol%.

Copolyamides PA2 contain in condensed form or consist of the following acid, diamine and lactam components:

as acid component S:

(a) 55 to 100 mol%, in particular 90 to 100 mol% terephthalic acid,

(b1) 0 to 45 mol%, in particular 0 to 10 mol% isophthalic acid,

as well as the diamine component D:

(c1) 0 to 59 mol%, in particular 0 to 23 mol% hexamethylenediamine, (c2) 60 to 99 mol%, in particular 75 to 98 mol% of at least one diamine of the formula H2N-A-NH2, as defined above , in particular at least one diamine of the formula H2N-A-NH2 which is selected from 1, 10-diamino-decane and 1, 12-diaminododecane;

(d) 1 to 40 mol%, in particular 2 to 20 mol% of at least one diamine of the formula H2N-Q-NH2, as defined above, in particular at least one diamine of the formula H2N-Q-NH2, which is selected from isophorone amine (IPDA; 3-aminomethyl-3,5,5-trimethylcyclohexylamine), bis (3-methyl-4-aminocyclohexyl) methane (MACM), 4,4 '- (aminocyclohexyl) methane (PACM), m-xylylenediamine and p-xylylenediamine and which is more preferably isophoronediamine, and optionally as Lactamkomponente L:

(e) 0 to 10 mol% or 0 to 5 mol% of one or more saturated, monocyclic lactams having 6 to 16 C atoms, as defined above, which is preferably selected from valerolactam, caprolactam and laurolactam and in particular comprising laurolactam or consisting of laurolactam;

wherein in each case the components a) and b1) and c1), c2) and d) together give 100 mol% and the component e) is based on the number of moles of the diamine component D. Preferred copolyamides PA2 contain in a condensed form or consist of the following acid and diamine components:

as acid component S:

(a) 90 to 100 mol%, in particular 95 to 100 mol% terephthalic acid, (b1) 0 to 10 mol%, in particular 0 to 5 mol% isophthalic acid,

- and as a diamine component D:

(c1) 0 to 23 mol%, in particular 0 to 15 mol% hexamethylenediamine, (c2) 75 to 98 mol%, in particular 80 to 95 mol% of at least one diamine of the formula H2N-A-NH2, as defined above , in particular at least one diamine of the formula H2N-A-NH2, which is selected from 1, 10-diamino-decane and 1, 12-diaminododecane;

(d) 2 to 20 mol%, in particular 5 to 15 mol%, of at least one diamine of the formula H2N-Q-NH2, as defined above, in particular at least one diamine of the formula H2N-Q-NH2, which is selected from isophoronedi amine (IPDA; 3-aminomethyl-3,5,5-trimethylcyclohexylamine), bis (3-methyl-4-aminocyclohexyl) methane (MACM), 4,4 '- (aminocyclohexyl) methane

(PACM), m-xylylenediamine and p-xylylenediamine and which is particularly preferably isophoronediamine,

wherein in each case the components a) and b1) and c1), c2) and d) together give 100 mol%.

Copolyamides PA3 contain in condensed form or consist of the following acid, diamine and lactam components:

as acid component S:

(a) 55 to 100 mol%, in particular 90 to 100 mol% terephthalic acid, (b1) 0 to 45 mol%, in particular 0 to 10 mol% isophthalic acid,

as the diamine component D:

(c1) 0 to 60 mol%, in particular 0 to 20 mol% hexamethylenediamine, (c2) 40 to 100 mol%, in particular 80 to 100 mol% of at least one diamine of the formula H2N-A-NH2, as defined above especially at least one diamine of the formula H2N-A-NH2 selected from 1, 10-diaminodecane and 1, 12-diaminododecane;

and as lactam component L:

(e) 1 to 30 mol%, in particular 1 to 15 mol% of one or more saturated, monocyclic lactams having 6 to 16 C atoms, as defined above, which is preferably selected from valerolactam, caprolactam and laurolactam and especially Laurinlactam comprises or consists of laurolactam;

in each case the components a) and b1) as well as c1) and c2) together give 100 mol% and the component e) is based on the number of moles of the diamine component D.

Preferred copolyamides PA3 contain in a condensed form or consist of the following acid, diamine and lactam components:

as acid component S:

(a) 90 to 100 mol%, in particular 95 to 100 mol% terephthalic acid,

(b1) 0 to 10 mol%, in particular 0 to 5 mol% isophthalic acid,

as the diamine component D:

(c1) 0 to 20 mol%, in particular 0 to 10 mol% of hexamethylenediamine, (c2) 80 to 100 mol%, in particular 90 to 100 mol% of at least one diamine of the formula H2N-A-NH2, such as defined above, in particular at least one diamine of the formula H2N-A-NH2, which is selected from 1, 10-diaminodecane and 1, 12-diaminododecane;

and as lactam component L:

(e) 1 to 15 mol% of one or more saturated monocyclic lactams having 6 to 16 carbon atoms, as defined above, which is preferably selected from valerolactam, caprolactam and laurolactam and which in particular comprises laurolactam or consists of laurolactam; in each case the components a) and b1) as well as c1) and c2) together give 100 mol% and the component e) is based on the number of moles of the diamine component D.

Copolyamides PA4 contain in condensed form or consist of the following acid, diamine and lactam components:

as acid component S:

as the diamine component D:

(c1) 55 to 79 mol%, in particular 60 to 73 mol% hexamethylenediamine, (c2) 20 to 45 mol%, in particular 25 to 40 mol% of at least one diamine of the formula H2N-A-NH2, as defined above , in particular at least a diamine of the formula H2N-A-NH2, which is selected from 1, 10-diamino-decane and 1, 12-diaminododecane;

(d) 1 to 20 mol%, in particular 2 to 20 mol%, of at least one diamine of the formula H 2 N-Q-NH 2, as defined above, in particular at least one diamine of the formula H 2 N-Q-NH 2, which is selected from isophorone amine (IPDA; 3-aminomethyl-3,5,5-trimethylcyclohexylamine), bis (3-methyl-4-aminocyclohexyl) methane (MACM), 4,4 '- (aminocyclohexyl) methane

(PACM), m-xylylenediamine and p-xylylenediamine, and more preferably isophoronediamine;

- and optionally as Lactamkomponente L:

(e) 0 to 10 mol% of one or more saturated, monocyclic lactams having 6 to 16 carbon atoms as defined above, which is preferably selected from valerolactam, caprolactam and laurolactam and which in particular comprises laurolactam or consists of laurolactam; wherein in each case the components a) and b1) and c1), c2) and d) together give 100 mol% and the component e) is based on the number of moles of the diamine component D.

The copolyamides according to the invention preferably have a melting temperature T _m (2) in the range from 540 to 605 K and in particular in the range from 550 to 595 K.

The copolyamides according to the invention preferably have a crystallization temperature Tk of at least 520 K, preferably of at least 530 K, in particular of at least 535 K. The crystallization temperature Tk will naturally not exceed the melting temperature and is generally at least 5 K below the melting temperature T _m (2).

The copolyamides according to the invention preferably have a heat of fusion ΔΗ (2) of at least 60 J / g, in particular at least 65 J / g and especially at least 70 J / g.

The copolyamides of the invention preferably have an amine end group content (AEG) of 50 to 100 mol / g. The copolyamides of the invention preferably have a viscosity number of 80 to 120 ml / g. The viscosity number (Staudinger function, denoted by VZ, VN or J) is defined as VZ = 1 / cx (η - n _s ) / n _s . The viscosity number is directly related to the mean molar mass of the copolyamide and gives information about the Workability of a plastic. The determination of the viscosity number can be carried out according to EN ISO 307 with an Ubbelohde viscometer.

The copolyamides according to the invention preferably have a number-average molecular weight M _n in a range from 13,000 to 25,000 g / mol, more preferably from 15,000 to 20,000 g / mol.

The copolyamide of the present invention preferably has a weight-average molecular weight Mw in a range of 25,000 to 125,000 g / mol.

The data of the number average molecular weight M _n and the weight average molecular weight M _w in the context of this invention relate to a determination by means of gel permeation chromatography (GPC). For calibration, PMMA is used as the polymer standard with a low polydispersity.

The copolyamides according to the invention preferably have a polydispersity PD (= Mw / Mn) of at most 6, in particular of at most 5 and particularly preferably of at most 3.5. The partly aromatic copolyamides according to the invention can in principle be prepared by customary methods known to the person skilled in the art. The preparation of partially aromatic polyamides usually begins with the formation of an aqueous salt solution of at least one diamine and at least one dicarboxylic acid. The formation of the salt solution is then followed by an oligomerization in the liquid aqueous phase. In the course of the further process, water must then be removed and the reaction temperature must be increased for the desired molecular weight increase. In principle, two alternative routes are available for further molecular weight buildup. In the first variant, the oligomer formed is converted by dehydration into the solid phase and subjected to a so-called solid state polymerization (solid state polymerization, SSP). In the second variant is carried out under controlled water separation and temperature increase, a transfer of the aqueous solution into the melt for further polycondensation. For further molecular weight buildup can then, if necessary, even a postpolymerization, z. B. in an extruder, connect.

In the following, some of the possible methods will be described with reference to the following documents, which can be applied in an analogous manner to the preparation of the partially aromatic copolyamides according to the invention, and the contents of which are fully incorporated in the disclosure of the present application.

A suitable method is z. As described in EP 0 693 515 A1. The preparation of precondensates of partially aromatic polyamides is carried out in a multistage batch process comprising the following steps a) to e): a) a salt formation phase for the preparation of salt (s) from diamine (s) and dicarboxylic acid (s) and optionally partial Pre-reaction to low molecular weight oligogamides at temperatures between 120 ° C and 220 ° C and pressures of up to 23 bar, b) optionally, the transfer of the solution from step a) in a second reaction vessel or a stirred autoclave below that at the end of their production c) the reaction phase during which the reaction is advanced to the precondensates by heating the reactor contents to a predetermined temperature and controlled adjustment of the water vapor partial pressure to a predetermined value, by controlled discharge of water vapor or optionally controlled feeding of water vapor a water connected to the autoclave d) a stationary phase to be maintained for at least 10 minutes, in which the temperature of the reactor contents and the water vapor partial pressure are each set to the values which are provided for the conversion of the precondensates into the subsequent process stage Precondensates of semicrystalline (co) polyamides having a melting point of more than 280 ° C, the temperature of the reactor contents during the phases c) and d) may not exceed 265 ° C and for said semicrystalline (co) polyamides during the phases c) and d) certain more precisely defined boundary conditions with respect to the dependence of the minimum water vapor partial pressure PH2O (minimum) to be observed on the temperature of the reactor contents and the amide group concentration of the polymer, and e) a discharge phase during which the precondensates are either directly in the

molten state or after passing through the solid state and if appropriate, further process stages can be fed to an end reaction device.

EP 0976774 A2 describes a process for preparing polyamides, comprising the following steps: i) polycondensation of a dicarboxylic acid component containing terephthalic acid and a diamine component in the presence of 15 to 35 wt .-% water at a reaction temperature of 250 to 280 ° C and a reaction pressure that satisfies the following equation:

P ₀ >P> 0.7 Po where Po is the saturated vapor pressure of water at the reaction temperature to obtain a primary polycondensate,

Discharging the primary polycondensate from step i) in an atmospheric environment with the same temperature range and at the same water content as in step i),

Molecular weight build-up by subjecting the effluent from step ii) to a percolation or melt polymerization. EP 0 129 195 A1 describes a process for the continuous preparation of polyamides, in which in an evaporator zone an aqueous solution of salts of dicarboxylic acids and diamines under elevated pressure with simultaneous evaporation of water and formation of a prepolymer to a temperature of 250 to 300 ° C heated, prepolymer and steam continuously separates, the vapors rectified and entrained diamines entrained, leading the prepolymer in a polycondensation zone and condensed under a pressure of 1 to 10 bar at a temperature of 250 to 300 ° C, wherein the aqueous salt solution under a Overpressure of 1 to 10 bar heated within a residence time of at most 60 seconds with the proviso that at exit from the evaporator zone, the degree of conversion is at least 93% and the water content of the prepolymer is at most 7 wt .-%.

EP 0 129 196 A1 describes a method comparable to EP 0 129 195 A1, in which the aqueous salt solution in the first third of a tubular pre-condensation zone provided with internals under an overpressure of 1 to 10 bar up to condenses a degree of conversion of at least 93% and in the remaining two-thirds of the precondensation zone brings the prepolymer and the vapor phase in intensive contact with each other. WO 02/28941 describes a continuous process for the hydrolytic polymerization of polyamides, comprising: a) polymerization of an aqueous salt solution of diacids and diamines under temperature and pressure conditions which are suitable for forming a multiphase reaction mixture, the reaction time however b) introducing heat into the reaction mixture while simultaneously reducing the pressure to remove water without the formation of solids, c) further polymerization of the dehydrated reaction mixture to the desired molecular weight.

US 4,019,866 describes a method and apparatus for continuous polyamide production. After the process, the polyamide-forming reactants are continuously pumped into a reaction zone designed to allow rapid heating and uniform mixing. The reactants are heated and uniformly mixed within the reaction zone for a predetermined hold time at an elevated temperature and pressure to form a vapor and a prepolymer. The formed vapor is continuously separated from the prepolymers and the prepolymers are withdrawn from the reaction zone. The device used is designed like a column and comprises a rectification zone, a first and a second reaction zone. In the first reaction zone, a polyamide-forming salt solution is partially vaporized and partially reacted, and in the second reaction zone, the reaction is continued at a lower pressure than in the first reaction zone. The vapor from the first reaction zone is vented through the rectification zone.

EP 0123377 A2 describes a condensation process which is used inter alia for the production of polyamides. Thereafter, a saline solution or prepolymer is expanded in an evaporative reactor at a relative pressure (gauge) of 0 to 27.6 bar. The residence time in the evaporation reactor is 0.1 to 20 seconds. In a special embodiment, first a prepolymerization takes place at a temperature of 191 to 232 ° C. and a solvent content (water content) of a few than 25% by weight: The resulting salt solution is then brought to a relative pressure of 103.4 to 206.8 bar, only then the temperature is raised to a value above the melting temperature and the solution is expanded. The polymer can be fed into a twin-screw extruder and subjected to polymerization at a residence time of about 45 seconds to 7 minutes.

DE 4329676 A1 describes a process for the continuous polycondensation of high molecular weight, in particular amorphous, partially aromatic copolyamides, wherein initially from an aqueous reaction mixture with heating and at least 15 bar pressure, a precondensate is prepared, followed by increasing the temperature and pressure, a prepolymer and finally by Condensation in a degassing extruder, the copolyamide is produced. In this case, the water content is reduced already in the precondensation stage and is at the end of the precondensation about 5 to 40 wt .-%. The preparation of the prepolymer then takes place at 220 to 350 ° C and a pressure of at least 20 bar. The post-polymerization is then carried out in a twin-screw extruder with degassing zones.

At least one catalyst can be used to prepare the copolyamides of the invention. Suitable catalysts are preferably selected from inorganic and / or organic phosphorus, tin or lead compounds and mixtures thereof.

As catalysts suitable tin compounds z. Tin (II) oxide, tin (II) hydroxide, tin (II) salts of mono- or polybasic carboxylic acids, e.g. Tin (II) dibenzoate, tin (II) di (2-ethylhexanoate), tin (II) oxalate, dibutyltin oxide, butylstannoic acid (C4Hg-

SnOOH), dibutyl tin dilaurate, etc. Suitable lead compounds are, for. Lead (II) oxide, lead (II) hydroxide, lead (II) acetate, basic lead (II) acetate, lead (II) carbonate, etc.

Preferred catalysts are phosphorus compounds such as phosphoric acid, phosphoric acid, hypophosphorous acid, phenylphosphonic acid, phenylphosphinic acid and / or salts thereof with mono- to tri-valent cations such as. B. Na, K, Mg, Ca, Zn or Al and / or their esters such. B. triphenyl phosphate, triphenyl phosphite or tris (nonylphenyl) phosphite. Particularly preferred as the catalyst hypophosphorous acid and its salts such as sodium hypophosphite.

The catalysts are preferably used in an amount of 0.005 to 2.5 parts by weight, based on the total weight of components a) to e). Particular preference is given to using hypophosphorous acid and / or a salt of hypophosphorous acid in an amount of from 50 to 1000 ppm, more preferably from 100 to 500 ppm, based on the total amount of components suitable for polyamide formation (= components a) to e)) ,

For controlling the molecular weight, at least one chain regulator can be used, which is preferably selected from monocarboxylic acids and monoamines. The chain regulator is preferably selected from acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, lauric acid, stearic acid, 2-ethylhexanoic acid, cyclohexanoic acid, benzoic acid, 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propanoic acid, 3 , 5-di-tert-butyl-4-hydroxybenzoic acid, 3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propanoic acid, 2- (3,5-di-tert-butyl-4-hydroxybenzylthio) acetic acid , 3,3-bis (3-tert-butyl-4-hydroxyphenyl) butanoic acid, butylamine, pentylamine, hexylamine, 2-ethylhexylamine, n-octylamine, n-dodecylamine, n-tetradecylamine, n-hexadecylamine, stearylamine, cyclohexylamine, 3- (cyclohexylamino) propylamine, methylcyclohexylamine, dimethylcyclohexylamine,

Benzylamine, 2-phenylethylamine, 2,2,6,6-tetramethylpiperidin-4-amine, 1, 2,2,6, 6-pentamethylpiperidin-4-amine, 4-amino-2,6-di-tert-butylamine butylphenol and mixtures thereof. It is also possible to use other monofunctional compounds as regulators which can react with an amino or acid group, such as anhydrides, isocyanates, acid halides or esters. The chain regulator can be added to the reaction mixture before or at the beginning of the oligomerization and / or the prepolymer before the postpolymerization. The usual amount of chain regulators used is in a range of 5 to 500 mmol per kg of polymer, preferably 10 to 200 mmol per kg of polymer.

In a specific embodiment, an aqueous composition of terephthalic acid a), hexamethylenediamine d) and optionally used, further polyamide-forming components (ie b), c) and e)) is provided for the preparation of the copolyamides of the invention and a salt formation subjected. If desired, other components such as catalysts, chain regulators and various additives can be added to this solution. Suitable additives are described in detail below in the case of the polyamide molding compositions. Among the additives that can be added already in the preparation of the polyamides according to the invention include, for. As antioxidants, light stabilizers, common processing aids, nucleating agents and crystallization accelerators. These can generally be added to the polyamides according to the invention in each stage of the preparation. It is also possible to use fillers and reinforcing substances already in the production of the polyamides according to the invention. Fillers and reinforcing agents are preferably added before and / or during the final postpolymerization. So these z. B. the copolyamides according to the invention in the Nachpoly- merisation be added in an extruder or kneader. In this case, it is advantageous if the extruder has suitable mixing elements, such as kneading blocks.

This composition provided for the preparation of the copolyamides according to the invention preferably has a water content of from 20 to 55% by weight, particularly preferably from 25 to 50% by weight, based on the total weight of the solution.

The preparation of the aqueous composition may be carried out in a conventional reaction apparatus, e.g. B. a stirred tank done. Preferably, the mixing of the components is carried out under heating. The preparation of the aqueous composition is preferably carried out under conditions in which essentially no oligomerization takes place. The temperature in the preparation of the aqueous composition in step a) is preferably in the range from 80 to 170.degree. C., more preferably from 100 to 165.degree. The preparation of the aqueous composition preferably takes place at ambient pressure or under elevated pressure. The pressure is preferably in the range from 0.9 to 50 bar, more preferably from 1 to 10 bar. In a specific embodiment, the preparation of the aqueous composition takes place at the autogenous pressure of the reaction mixture. The preparation of the aqueous composition can be carried out in an inert gas atmosphere. Suitable inert gases are for. As nitrogen, helium or argon. In many cases, complete inerting is not required, but rinsing the reaction device with an inert gas before heating the components is sufficient. In a suitable procedure for preparing the aqueous composition, the diamine component is initially charged in at least part of the water in the reaction apparatus. Subsequently, the remaining components are added, preferably with stirring, and the water content is adjusted to the desired amount. The reaction mixture is heated with stirring until a clear homogeneous solution has formed. The aqueous composition thus obtained is preferably substantially at the production temperature, i. H. without an intermediate cooling, used for the oligomerization.

The oligomerization to form prepolymers and the postpolymerization to the molecular weight can be carried out by conventional methods known in the art. Some examples of such methods have already been mentioned above.

The polycondensates obtained in the preparation of the partially aromatic copolyamides according to the invention can be comminuted before processing into polyamide molding compositions, for example into granules. For example, the copolyamide obtained in the polycondensation may first be formed into one or more strands and then subjected to granulation. For this purpose, known to the expert devices can be used, for. B. extruder, the discharge side z. As perforated plates, nozzles or nozzle plates. Preferably, the partially aromatic copolyamide obtained in the polycondensation is formed into strands in a flowable state and subjected to granulation as a flowable strand-like reaction product or after cooling.

Another object of the invention is a polyamide molding composition containing at least one partially aromatic copolyamide according to the invention.

Preference is given to a polyamide molding composition comprising:

A) from 25 to 100% by weight of at least one partially aromatic copolyamide, as defined above,

B) 0 to 75% by weight of at least one filler and reinforcing material,

C) 0 to 50 wt .-% of at least one additive, wherein the components A) to C) together give 100 wt .-%. The term "filler and reinforcing material" (= component B) is broadly understood in the context of the invention and includes particulate fillers, fibrous materials and any transitional forms. Particulate fillers can have a wide range of particle sizes, ranging from dusty to coarse-grained particles. Suitable fillers are organic or inorganic fillers and reinforcing materials. For example, inorganic fillers such as kaolin, chalk, wollastonite, talc, calcium carbonate, silicates, titanium dioxide, zinc oxide, graphite, glass particles, e.g. Glass beads, nanoscale fillers such as carbon nanotubes, carbon black, nanoscale phyllosilicates, nanoscale aluminum oxide (Al 2 O 3), nanoscale titanium dioxide (TIO 2), graphene, permanently magnetic or magnetizable metal compounds and / or alloys , Phyllosilicates and nanoscale silica (S1O2). The fillers may also be surface-treated.

As sheet silicates in the molding compositions of the invention z. As kaolins, Serpentine, talc, mica, vermiculite, lllite, smectites, montmorillonite, hectorite, double hydroxides or mixtures thereof. The layered silicates may be surface treated or untreated.

Furthermore, one or more fibers can be used. These are preferably selected from known inorganic reinforcing fibers, such as Borfa- fibers, carbon fibers, silica fibers, ceramic fibers and basalt fibers; organic reinforcing fibers such as aramid fibers, polyester fibers, nylon fibers, polyethylene fibers and natural fibers such as wood fibers, flax fibers, hemp fibers and sisal fibers.

Particularly preferred is the use of glass fibers, carbon fibers, aramid fibers, boron fibers, metal fibers or potassium titanate fibers.

Specifically, chopped glass fibers are used. In particular, component B) comprises glass and / or carbon fibers, short fibers preferably being used. These preferably have a length in the range of 2 to 50 mm and a

Diameter of 5 to 40 μηη on. Alternatively, continuous fibers (rovings) can be used. Fibers having a circular and / or non-circular cross-sectional area are suitable. In the latter case, the dimensional ratio of the main cross-sectional axis to the secondary cross-sectional axis is in particular> 2, preferably in the range of 2 to 8 and particularly preferably in the range of 3 to 5.

In a specific embodiment, component B) comprises so-called "flat glass fibers". These have in particular an oval or elliptical or a constriction (s) provided elliptical (so-called "cocoon" or "cocoon" fiber) or rectangular or nearly rectangular cross-sectional area. In this case, glass fibers having a non-circular cross-sectional area and a dimensional ratio of the main cross-sectional axis to the minor cross-sectional axis of more than 2, preferably from 2 to 8, in particular from 3 to 5, are preferably used.

To reinforce the molding compositions according to the invention it is also possible to use mixtures of glass fibers of circular and non-circular cross-section. In a specific embodiment, the proportion of flat glass fibers, as defined above, d. H. they make up more than 50% by weight of the total mass of the fibers.

When used as component B) rovings of glass fibers, these preferably have a diameter of 10 to 20 μηη, preferably from 12 to 18 μηη, on. The cross section of the glass fibers can be round, oval, elliptical, almost rectangular or rectangular. Particularly preferred are so-called flat glass fibers with a ratio of the cross-sectional axes of 2 to 5. In particular

E-glass fibers used. But it can also all other types of glass fiber, such. As A, C, D, M, S, R glass fibers or any mixtures thereof or mixtures with E-glass fibers are used. The polyamide molding compositions according to the invention can be prepared by the known processes for producing long-fiber-reinforced rod granules, in particular by pultrusion processes in which the endless fiber strand (roving) is completely impregnated with the polymer melt and then cooled and cut. The long fiber-reinforced rod granules obtained in this way, which preferably has a granule length of 3 to 25 mm, in particular of 4 to 12 mm, can, with the usual processing methods, such as. As injection molding or pressing, to be processed into moldings. The novel polyamide molding compositions preferably contain from 25 to 75% by weight, more preferably from 33 to 60% by weight, of at least one filler and reinforcing material B), based on the total weight of the polyamide molding composition.

Suitable additives C) are heat stabilizers (flame retardants), light stabilizers (UV stabilizers, UV absorbers or UV blockers), lubricants, dyes, nucleating agents, metallic pigments, metal flakes, metal-coated particles, antistatic agents, conductive additives, mold release agents, optical brighteners, Defoamer, etc.

As component C), the molding compositions according to the invention preferably contain 0.01 to 3 wt .-%, more preferably 0.02 to 2 wt .-%, in particular 0.1 to

1, 5 wt .-% of at least one heat stabilizer.

The heat stabilizers are preferably selected from copper compounds, secondary aromatic amines, sterically hindered phenols, phosphites, phosphonites and mixtures thereof.

If a copper compound is used, the amount of copper is preferably 0.003 to 0.5, in particular 0.005 to 0.3 and particularly preferably 0.01 to 0.2 wt .-%, based on the sum of components A) to C) ,

If stabilizers based on secondary aromatic amines are used, the amount of these stabilizers is preferably 0.2 to 2% by weight, particularly preferably 0.2 to 1.5% by weight, based on the sum of the components A). to C).

If stabilizers based on sterically hindered phenols are used, the amount of these stabilizers is preferably 0.1 to 1.5% by weight, particularly preferably 0.2 to 1% by weight, based on the sum of the components A). to C). If stabilizers based on phosphites and / or phosphonites are used, the amount of these stabilizers is preferably from 0.1 to 1, 5 wt .-%, particularly preferably from 0.2 to 1 wt .-%, based on the sum of Components A) to C).

For example, compounds of mono- or divalent copper, e.g. As salts of monovalent or divalent copper with inorganic or organic acids or mono- or dihydric phenols, the oxides of mono- or divalent copper or the complex compounds of copper salts with ammonia, amines, amides, lactam men, cyanides or phosphines, preferably Cu (I) or Cu (II) salts of hydrohalic acids, hydrocyanic acids or the copper salts of aliphatic carboxylic acids used. Particularly preferred are the monovalent copper compounds CuCl, CuBr, Cul, CuCN and CU2O, and the divalent copper compounds CuC, CuS0 ₄ , CuO, copper (II) acetate or copper (II) stearate.

The copper compounds are commercially available or their preparation is known in the art. The copper compound can be used as such or in the form of concentrates. Concentrate is to be understood as meaning a polymer, preferably of the same chemical nature as component A), which contains the copper salt in high concentration. The use of concentrates is a common method and is particularly often used when very small amounts of a feedstock are to be dosed. Advantageously, the copper compounds in combination with other metal halides, in particular alkali metal halides, such as Nal, Kl, NaBr, KBr, used, wherein the molar ratio of metal halide to copper halide from 0.5 to 20, preferably 1 to 10 and particularly preferably 3 to 7, is ,

Particularly preferred examples of stabilizers based on secondary aromatic amines which can be used according to the invention are adducts of phenylenediamine with acetone (Naugard A), adducts of phenylenediamine with linolenic acid, Naugard® 445,

N, N'-dinaphthyl-p-phenylenediamine, N-phenyl-N'-cyclohexyl-p-phenylenediamine or mixtures of two or more thereof.

Preferred examples of stabilizers based on sterically hindered phenols which can be used according to the invention are N, N'-hexamethylene-bis-3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionamide, bis (3, 3-bis- (4'-hydroxy-3'-tert-butylphenyl) -butanoic 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, diphenyl alkyl phosphite, phenyl dialkyl phosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl phthaloerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, diisopropylpentaerythritol 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, tristearyl sorbitol triphosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylene diphosphonite, 6-isoctyloxy-2,4,8,10 tetra-tert-butyl-12H-dibenz [d, g] -1, 3,2-dioxaphosphocine, 6-fluoro-2, 4,8,10-tetra-tert-butyl-12-methyl-dibenz [i.e. , g] -1, 3,2-dioxaphosphocine, bis (2,4-di-tert-butyl-6-methylphenyl) methyl phosphite and bis (2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite. In particular, 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 (Hostanox® PAR24: commercial product from BASF Se).

A preferred embodiment of the heat stabilizer is the combination of organic heat stabilizers (in particular Hostanox PAR 24 and Irganox 1010), a bisphenol A based epoxide (especially Epikote 1001) and a copper stabilization based on Cul and Kl. A commercially available stabilizer mixture consisting from organic stabilizers and epoxides is, for example, Irgatec NC66 from BASF SE. Particularly preferred is a heat stabilization based solely on Cul and Kl. In addition to the addition of copper or copper compounds, the use of other transition metal compounds, in particular metal salts or metal oxides of group VB, VIB, VIIB or VIIIB of the Periodic Table excluded. In addition, the molding composition according to the invention preferably no transition metals of group VB, VIB, VIIB or VIIIB of the Periodic Table, such. As iron or steel powder added.

The novel molding materials preferably comprise 0 to 30% by weight, more preferably 0 to 20% by weight, based on the total weight of components A) to C), of at least one flameproofing agent as additive C). If the molding compositions according to the invention contain at least one flame retardant, preferably in an amount of 0.01 to 30 wt .-%, particularly preferably from 0.1 to 20 wt .-%, based on the total weights of components A) to C). Suitable flame retardants C) include halogen-containing and halogen-free flame retardants and their synergists (see also Gächter / Müller, 3rd edition 1989 Hanser Verlag, Chapter 1 1). Preferred halogen-free flame retardants are red phosphorus, phosphinic or diphosphinic acid salts and / or nitrogen-containing FS agents such as melamine, melamine cyanurate, melamine sulfate, melamine borate, oxalate, phosphate (prim, sec.) or pyrophosphate sec, Neopentylglycolborsäuremelamin, guanidine and the skilled worker known derivatives thereof, and polymeric melamine phosphate (CAS No .: 56386-64-2 or 218768-84-4 and EP 1095030), ammonium polyphosphate (optionally also in admixture with ) Trishydroxyethyl isocyanurate (EP 584567). Further N-containing or P-containing or PN condensates as suitable flame retardants can be found in DE 10 2004 049 342, as well as the usual synergists for this purpose, such as oxides or borates. Suitable halogen-containing flame retardants are, for. B. oligomeric brominated polycarbonates (BC 52 Great Lakes) or Polypentabrombenzylac- rylate with N greater than 4 (FR 1025 dead sea bromine), reaction products of tetrabromob-phenol-A with epoxides, brominated oligomeric or polymeric styrenes, dechlorinated , which are usually used with antimony oxides as synergists (for details and other flame retardants: see DE-A-10 2004 050 025).

As antistatic agents in the molding compositions of the invention z. As carbon black and / or carbon nanotubes can be used. However, the use of carbon black can also serve to improve the black color of the molding composition. However, the molding composition may also be free of metallic pigments.

Furthermore, the present invention relates to molded articles which are produced using the copolyamides or polyamide molding compositions according to the invention.

The partially aromatic polyamides according to the invention are advantageously suitable for use in the production of molded parts for electrical and electronic components and for automotive applications in the high-temperature range.

A specific embodiment are moldings in the form or as part of a component for the automotive sector, in particular selected from cylinder head covers, engine covers, intercooler housings, intercooler flaps, intake manifolds, intake manifolds, connectors, gears, fan wheels, cooling water boxes, housings or housing parts for heat exchangers, coolant radiators, intercoolers , Thermostats, Water pumps, Radiators, Fasteners.

A further specific embodiment are shaped bodies as or as part of an electrical or electronic passive or active component, a printed circuit board, a part of a printed circuit board, a housing component, a foil, a conduit, in particular in the form of or as part of a switch, a plug, a jack, a distributor, a relay, a resistor, a capacitor, a coil or a bobbin, a lamp, a diode, an LED, a transistor, a Connector, a controller, an integrated circuit (IC), a processor, a controller, a memory and / or a sensor.

The partially aromatic polyamides according to the invention are furthermore particularly suitable for use in soldering processes under lead-free conditions, for the production of connectors, microswitches, micro-probes and semiconductor components, in particular reflector housings of light-emitting diodes (LED).

A special embodiment are shaped bodies as fastening elements of electrical or electronic components, such as spacers, bolts, strips, slide-in guides, screws and nuts.

Particularly preferred is a molded part in the form or as part of a base, a connector, a plug or a socket. The molded part preferably contains functional elements which require mechanical toughness. Examples of such functional elements are film hinges, snap-in hooks and spring tongues.

Inside the car, there is a use for dashboards, steering column switches, seat parts, headrests, center consoles, gearbox components and door modules, in the outer door compartment for door handles, exterior mirror components, windscreen wiper components, windscreen wiper housings, grilles, roof rails, sunroof frames, engine covers, cylinder head covers, intake manifolds, windscreen wipers and bodywork exterior parts possible. For the kitchen and household sector, the use of flow-improved polyamides for the production of components for kitchen appliances, such. As fryers, irons, knobs, and applications in the garden leisure area, z. B. components for irrigation systems or garden tools and door handles possible. The following examples serve to illustrate the invention without limiting it in any way.

EXAMPLES The copolyamides were prepared by condensation in the melt in a pressure autoclave equipped with a stirrer. The respective diamines and dicarboxylic acids and optionally lactams were weighed in and then admixed with 15% by weight of water and 0.03% by weight of sodium hypophosphite as catalyst. After purging the autoclave with nitrogen several times, the Outside temperature set to 345 ° C. After the pressure inside the autoclave had reached 40 bar, the pressure was released to ambient pressure within 28 minutes. The copolymer thus obtained is postcondensed under constant nitrogen flow for 15 minutes and then discharged through the outlet valve as a strand and granulated.

The crystallization temperatures (Tk), melting temperatures (T _m (2)) and heat of fusion (ΔΗ (2)) contained in Table 1 were determined by differential scanning calorimetry (DSC) according to the method described above in accordance with DIN EN ISO 1 1357-3 , The DSC measurement was repeated once each, with the sample held at melt temperature for 5 minutes to ensure a defined thermal history of the polyamide. This is indicated by the index "2" on the measured values of the melting temperature and the heat of fusion. It was measured under nitrogen in open aluminum crucibles at a heating rate and cooling rate of 20 K / min.

The following abbreviations were used:

HMD hexamethylenediamine

DDAc 1, 12-dodecanedioic acid

DDA 1, 10-decanediamine

DDDA 1, 12-dodecanediamine

T terephthalic acid

I isophthalic acid

IPDA isophorone diamine

MXDA m-xylylenediamine

CL caprolactam

5-1 2-methyl-1,5-diaminopentane

6.T / 12.T Copolyamide of HMD, T and DDDA

6.T / 10.T Copolyamide of HMD, T and DDA

6.T / 6.12 Copolyamide of HMD, T and DDAc

12.T / MXDA.T copolyamide from MXD, T and DDDA

12.T / IPDA.T copolyamide from MXD, T and DDDA

12.T / 6 copolyamide from CL, T and DDDA

6.T / 5-1 .T Copolyamide of HMD, T and 5-1 Table 1

Example no. Composition ^1> T _k T m (2) T _m (2) - T _k ΔΗ (2)

Polyamide [° C] [° C] [K] [Y / g]

V1 6.T / 6.I 320 270 50 57

T: I = 70: 30

1 6.T / 12.T 317 280 37 75

HMD: DDDA = 60: 40

2 6.T / 10.T 324 291 33 63

HMD: DDA = 70:30

3 6.T / 10.T 334 304 30 85

HMD: DDA = 90:10

4 6.T / 6.12 347 324 23 82

T: DDAc = 95: 5

5 6.T / 6.12 326 287 39 69

T: DDAc = 80:20

6 6.T / 6.12 302 368 34 72

T: DDAc = 60: 40

7 12.T / MXDA.T 292 268 24 91

DDDA: MXDA = 95: 5

8 12.T / MXDA.T 289 260 29 75

DDDA: MXDA = 90: 10

9 12.T / MXDA.T 270 230 40 55

DDDA: MXDA = 80:20

10 12.T / IPDA.T 289 270 19 89

DDDA: IPDA = 95: 5

1 1 12.T / IPDA.T 287 261 26 77

DDDA: IPDA = 90:10

12 12.T / IPDA.T 275 247 28 64

DDDA: IPDA = 80:20

13 12.T / 6 291 276 15 83

CL 10 mol%

14 12.T / 6 287 273 14 87

CL 10 mol%

15 12.T / 6 283 267 16 81

CL 10 mol%

16 6.T / 5-1 325 308 17 76

HMD: 5-1 70:30

Claims

claims

1 . Partially aromatic copolyamide PA based on terephthalic acid and aliphatic diamines, which has at least 55 mol% of repeating units derived from terephthalic acid amides, and which has a melting enthalpy

ΔΗ (2) of at least 55 J / g and in particular at least 60 J / g, wherein the difference T _m (2) - T _{k is} not more than 40 K, in particular not more than 35 K,

T _m (2) means the melting temperature in Kelvin and

T _{k is} the crystallization temperature in Kelvin, where

the melting enthalpy ΔΗ (2), the crystallization temperature Tk and the melting temperature T _m (2) were determined by means of DSC on a thermally conditioned sample of copolyamide PA.

Copolyamide according to Claim 1, selected from polyamides PA1, PA2, PA3 and PA4,

wherein the polyamides contain PA1 in a condensed form: as the acid component S:

(a) 55 to 100 mole percent terephthalic acid, and

(b1) 0 to 45 mol% isophthalic acid,

(b2) 0 to 45 mol% of one or more dicarboxylic acids of the formula

HO2C-B-CO2H, in which B is an alkanediyl radical having 6 to 14 C atoms,

as the diamine component D:

(c1) 55 to 100 mol% hexamethylenediamine,

(c2) 0 to 45 mol% of one or more diamines of the formula H2N-A-NH2, where A is an alkanediyl radical having 8 to 16 C atoms;

and optionally as Lactamkomponente L:

(e) 0 to 10 mol% of one or more saturated, monocyclic

Lactams having 6 to 16 C atoms;

in each case the components a), b1) and b2) and c1) and c2) together give 100 mol%, the component e) is based on the molar number of the amine component D and wherein the polyamide at least one of the components b2) and c2) in an amount of at least 5 mol% condensed;

wherein the polyamides contain PA2 in a condensed form: as the acid component S:

(a) 55 to 100 mole percent terephthalic acid, and

(b1) 0 to 45 mol% isophthalic acid, as well as the diamine component D:

(c1) 0 to 59 mol% hexamethylenediamine,

(c2) 60 to 99 mol% of at least one diamine of the formula H2N-A-NH2, where A is an alkanediyl radical having 8 to 16 C atoms;

(d) 1 to 40 mol% of at least one diamine of the formula H2N-Q-NH2, in which Q is a saturated alicyclic or araliphatic hydrocarbon radical having 8 to 18 carbon atoms,

and optionally as Lactamkomponente L:

(e) 0 to 10 mol% of one or more saturated, monocyclic lactams having 6 to 16 carbon atoms;

wherein in each case the components a) and b1) and c1), c2) and d) together give 100 mol% and the component e) is based on the number of moles of the diamine component D;

wherein the polyamides contain PA3 in a condensed form:

as acid component S:

(a) 55 to 100 mole percent terephthalic acid, and

(b1) 0 to 45 mol% isophthalic acid,

as the diamine component D:

(c1) 0 to 60 mol% hexamethylenediamine,

(c2) 40 to 100 mol% of at least one diamine of the formula H2N-A-NH2, where A is an alkanediyl radical having 8 to 16 carbon atoms;

and as lactam component L:

(e) 1 to 30 mol% of one or more saturated, monocyclic lactams having 6 to 16 carbon atoms;

wherein in each case the components a) and b1) and c1) and c2) together

100 mol% yield and the component e) based on the number of moles of the diamine component D; and

the polyamides containing PA4 in a condensed form:

as acid component S:

(a) 55 to 100 mole percent terephthalic acid, and

(b1) 0 to 45 mol% isophthalic acid,

as the diamine component D:

(c1) 55 to 79 mol% hexamethylenediamine,

(c2) 20 to 44 mol% of at least one diamine of the formula H2N-A-NH2, where A is an alkanediyl radical having 8 to 16 C atoms;

(d) 1 to 20 mol% of at least one diamine of the formula H2N-Q-NH 2, in which Q is a saturated alicyclic or araliphatic hydrocarbon radical having 8 to 18 C atoms, (e) 0 to 10 mol% of one or more saturated, monocyclic

Lactams with 6 to 16 carbon atoms

in each case the components a) and b1) as well as c1), c2) and d) together give 100 mol% and the component e) is based on the number of moles of the diamino component D.

3. copolyamide according to claim 2, wherein the diamine of the formula H2N-A-NH2 is selected from 1, 9-nonanediamine, 1, 10-diaminodecane and 1, 12-diaminododecane.

A copolyamide according to claim 2 or 3, wherein the dicarboxylic acid of the formula HO 2 C-B -CO 2 H is selected from sebacic acid, 1, 12-dodecanedioic acid and 1, 14-tetradecanedioic acid.

A copolyamide according to claim 2, 3 or 4, wherein the lactam is selected from valerolactam, caprolactam and laurolactam.

Copolyamide according to claim 2, 3, 4 or 5, wherein the diamine of the formula

H2N-Q-NH2 is selected from isophorone diamine (IPDA), bis (3-methyl-4-aminocyclohexyl) methane (MACM), 4,4 '- (aminocyclohexyl) methane (PACM), m-xylylenediamine, p-xylylenediamine and Mixtures thereof.

Copolyamide PA1 according to one of claims 2 to 5, consisting of a condensed form

(a) 90 to 100 mole percent terephthalic acid, and

(b1) 0 to 10 mol% isophthalic acid,

(b2) 0 to 10 mol% of a dicarboxylic acid of the formula HO 2 C-B-CO 2 H, where B is an alkanediyl radical having 6 to 14 C atoms,

(c1) 55 to 98 mol% hexamethylenediamine,

(c2) from 2 to 45 mol% of at least one diamine of the formula H2N-A-NH2, wherein A is an alkanediyl radical having 8 to 16 carbon atoms;

(e) 0 to 10 mol% of one or more saturated, monocyclic lactams having 6 to 16 carbon atoms.

(a) 55 to 98 mole percent terephthalic acid, and

(b1) 0 to 10 mol% isophthalic acid,

(b2) from 2 to 45 mol% of at least one dicarboxylic acid of the formula HO 2 C-B-CO 2 H, where B is an alkanediyl radical having 6 to 14 C atoms, (c1) 90 to 100 mol% of hexamethylenediamine,

(c2) 0 to 10 mol% of one or more diynes of the formula H2N-A-NH2, in which

A is an alkanediyl radical having 8 to 16 C atoms;

Copolyamide PA2 according to one of claims 2 to 5, consisting in a condensed form

(a) 90 to 100 mole percent terephthalic acid, and

(b1) 0 to 10 mol% isophthalic acid,

(c1) 0 to 23 mol% hexamethylenediamine,

(c2) 75 to 98 mol% of at least one diamine of the formula H2N-A-NH2, in which A is an alkanediyl radical having 8 to 16 C atoms;

(d) 2 to 20 mol% of at least one diamine of the formula H2N-Q-NH2, wherein Q is a saturated alicyclic or araliphatic hydrocarbon radical having 8 to 18 carbon atoms

(e) 0 to 10 mol% of one or more saturated, monocyclic lactams having 6 to 16 carbon atoms. 10. copolyamide PA3 according to any one of claims 2 to 5, consisting in a condensed form

(a) 90 to 100 mole percent terephthalic acid, and

(b1) 0 to 10 mol% isophthalic acid,

(c1) 0 to 20 mol% hexamethylenediamine,

(c2) 80 to 100 mol% of at least one diamine of the formula H2N-A-NH2, wherein

A is an alkanediyl radical having 8 to 16 C atoms;

(e) 1 to 15 mol% of one or more saturated, monocyclic lactams having 6 to 16 carbon atoms.

Copolyamide PA3 according to claim 10, wherein the monocyclic lactam comprises or consists of lauric lactam.

Copolyamide PA4 according to one of claims 2 to 5, consisting in a condensed form

(a) 55 to 100 mole percent terephthalic acid, and

(b1) 0 to 45 mol% isophthalic acid,

(c1) 60 to 73 mol% hexamethylenediamine,

(c2) 25 to 40 mol% of at least one diamine of the formula H2N-A-NH2, where A is an alkanediyl radical having 8 to 16 C atoms; (d) 2 to 20 mol% of at least one diamine of the formula H2N-Q-NH2, in which Q is a saturated alicyclic or araliphatic hydrocarbon radical having 8 to 18 carbon atoms,

13. Copolyamide according to one of the preceding claims, wherein the molar ratio of the acid component S to the amine component D in the range of 0.95: 1 to 1, 1: 1.

14. Copolyamide according to one of the preceding claims, which has at least one of the following features:

(1) a crystallization temperature Tk of at least 520 K;

(2) a melting temperature T _m (2) in the range of 540 to 605 K;

(3) a difference T _m (2) - T _k in the range of 10 to 40 K; and or

(4) a heat of fusion ΔΗ (2) of at least 70 J / g.

A polyamide molding composition containing at least one copolyamide as defined in any one of claims 1 to 14.

16 molded body made of a polyamide molding composition according to claim 15.

17. A method of identifying a partially aromatic copolyamide based on terephthalic acid and aliphatic diamines which has at least 55 mole% repeat units derived from terephthalic acid amides, the good elevated temperature mechanical properties and, at the same time, improved processability, especially in thermoplastic molding processes , characterized in that the melting enthalpy ΔΗ (2), the crystallization temperature Tk and the melting temperature T _m (2) are determined by means of DSC on a thermally conditioned sample of the copolyamide PA and a polyamide is selected which has a melting enthalpy ΔΗ (2) of at least 55 J / g and in particular at least 60 J / g and wherein the difference

T _m (2) - T _{k is} not more than 40 K, in particular not more than 35 K.