Thermoplastic molding compositions based on polyamides and thermoplastic polyester elastomers

Thermoplastic molding compositions are obtainable by mixing PA0 A) from 0.5 to 5% by weight of a thermoplastic polyester elastomer and PA0 B) from 0 to 50% by weight of fibrous or particulate fillers or mixtures thereof into a melt of PA0 C) from 40 to 99.5% by weight of a polyamide prepolymer having a viscosity number of from 40 to 80 ml/g and subsequent postcondensation in solid phase.

The present invention relates to thermoplastic molding compositions 
obtainable by mixing 
A) from 0.5 to 5% by weight of a thermoplastic polyester elastomer and 
B) from 0 to 50% by weight of fibrous or particulate fillers or mixtures 
thereof into a melt of 
C) from 40 to 99.5% by weight of a polyamide prepolymer having a viscosity 
number of from 40 to 80 ml/g and subsequent postcondensation in solid 
phase. 
The present invention also relates to processes for preparing these 
thermoplastic molding compositions, to the use thereof for producing 
fibers, films and moldings, and to the moldings thus obtainable. 
Polyamides such as poly-.epsilon.-caprolactam and 
polyhexamethyleneadipamide are well known engineering plastics and have 
found application in many fields. In general they possess great hardness, 
stiffness and good heat resistance, they are resistant to abrasion and 
wear and also to many chemicals, and they are flame-resistant. 
In the processing of polyamides, in particular in injection molding, it is 
generally customary to add lubricants to improve the feed and demolding 
characteristics. 
For instance, DE-A-37 06 356 describes polyamide granules with an outer 
lubricant coating comprising zinc stearate, aluminum stearate, calcium 
stearate and C.sub.2 -C.sub.24 -esters of aliphatic carboxylic acids of 
from 6 to 24 carbon atoms. 
DE-A-23 49 835 discloses the addition of calcium stearate or zinc stearate 
to polyamide molding compositions. 
However, the addition of these lubricants leads to a molecular weight 
degradation, associated with a toughness loss in the processing of 
polyamides, in particular at elevated temperature. This effect is 
particularly pronounced with high-melting polyamides such as copolyamides 
of .epsilon.-caprolactam, hexamethylenediamine and terephthalic acid and 
of tetramethylenediamine and adipic acid. But these disadvantages are also 
found in polyamides of hexamethylenediamine and adipic acid, especially on 
addition of aluminum stearate. Moreover, the addition of these lubricants 
robs the polyamides of their flame-resistance. 
The use of stearic acid, stearyl stearate, pentaerythritol and diglycol 
esters of long-chain fatty acids, palmitic acid, behenic acid and 
derivatives thereof as lubricants is likewise known. These compounds 
likewise have the abovementioned disadvantages. 
If these lubricants are incorporated into a melt of a polyamide prepolymer 
having a viscosity number of from 40 to 80 ml/g and this mixture is 
subjected to a thermal aftertreatment to obtain the viscosity numbers of 
not less than 140 ml/g necessary for engineering applications, they are 
extracted at the prevailing processing temperatures and thus become 
ineffective. 
Examples of lubricants which are not based on derivatives of long-chain 
fatty acids are polytetrafluoroethylene, molybdenum sulfide and graphite. 
Their disadvantages are in particular the dark self-color and economic and 
health aspects. 
JP-A2-106 854/85 describes polyamides containing a mixture of acrylate 
rubbers and polyether esters as impact modifying components. However, 
these products are very soft and readily flammable. 
DE-A-39 26 895 discloses the addition of a mixture of polyether esters and 
aluminum salts to polyamides. This again has the aforementioned 
disadvantages of the molecular weight degradation of the polyamides due to 
the use of aluminum salts and the extraction of the lubricants on 
incorporation thereof into a polyamide prepolymer having a viscosity 
number of from 40 to 80 ml/g at the prevailing processing temperatures. 
EP-A-331 001 describes the addition of polyether esters to improve the 
flowability of polyamides. However, these processes lead to products which 
are not flame-resistant. 
It is an object of the present invention to provide polyamide-based 
thermoplastic molding compositions which do not have the afore-described 
disadvantages and which shall possess in particular good flowability and 
flame resistance. 
We have found that this object is achieved according to the present 
invention by the thermoplastic molding compositions defined at the 
beginning. Preferred compositions of this kind are revealed in the 
subclaims. 
We have also found processes for preparing these thermoplastic molding 
compositions, the use thereof for producing fibers, films and moldings, 
and the moldings thus obtainable. 
Component A) of the thermoplastic molding compositions of the present 
invention comprises from 0.5 to 5% by weight, preferably from 1.5 to 2.5% 
by weight, of a thermoplastic polyester elastomer. 
For the purposes of the present invention polyester elastomers are 
segmented copolyether esters which contain long-chain segments which in 
general are derived from poly(alkylene ether) glycols and short-chain 
segments which are derived from low molecular weight diols and 
dicarboxylic acids. 
Such products are known per se and described in the literature. By way of 
example there may be mentioned U.S. Pat. Nos. 3,651,014, 3,784,520, 
4,185,003 and 4,136,090 and some papers by G. K. Hoeschele (Chimia 28 (9) 
(1974), 544; Angew. Makromolek. Chemie 58/59 (1977), 299-319; and Pol. 
Eng. Sci. 1974, 848). Products of this type are also commercially 
available under the designations Hytrel.RTM. (DuPont), Arnitel.RTM. (Akzo) 
and Pelprene.RTM. (Toyobo Co. Ltd.). 
In general, thermoplastic copolyether ester elastomers are composed of 
long-chain segments of the formula 
##STR1## 
and short-chain segments of the formula 
##STR2## 
where G is a divalent radical which is formed on removing the terminal 
hydroxyl groups of a poly(alkylene oxide) glycol having a molecular weight 
of preferably 400-6000, in particular 600-4000, 
D is a divalent radical which is formed on removing the terminal hydroxyl 
groups of a low molecular weight diol having a molecular weight of 
preferably less than 250, and 
R is a divalent radical which is formed on removing the carboxyl groups of 
a dicarboxylic acid having a molecular weight of preferably less than 300. 
The molecular weight in question here is the number average molecular 
weight. 
It will be readily understood that it is also possible to use mixtures of a 
plurality of poly(alkylene oxide) glycols, a plurality of diols or a 
plurality of dicarboxylic acids. 
The poly(alkylene oxide) glycols HO--G--OH preferably have a melting point 
of less than 55.degree. C. and a carbon/oxygen molar ratio of preferably 
from 2 to 10, in particular from 2 to 6. 
Examples of poly(alkylene oxide) glycols are poly(ethylene oxide) glycol, 
poly(1,2-propylene oxide)glycol, poly(1,3-propylene oxide) glycol, 
poly(1,2-butylene oxide) glycol, poly(1,3-butylene oxide) glycol, 
poly(1,4-butylene oxide) glycol, poly(pentamethylene oxide) glycol, 
poly(hexamethylene oxide) glycol, poly(heptamethylene oxide) glycol, 
poly(octamethylene oxide) glycol, poly(nonamethylene oxide) glycol and 
also random or block copolymers of various of the aforementioned glycols. 
Preference is given to poly(ethylene oxide) glycol, poly(1,2-propylene 
oxide) glycol, poly(1,3-propylene oxide) glycol and poly(1,4-butylene 
oxide) glycol and mixtures thereof. The weight proportion of the 
long-chain segments which are derived from the foregoing polyalkylene 
oxide glycols and dicarboxylic acids is in general within the range from 5 
to 70% by weight, preferably from 7 to 50% by weight, based on the total 
weight of component A). 
Suitable diols HO-D-OH are in general low molecular weight diols having 
molecular weights of preferably less than 250. They can have a linear or 
branched, cycloaliphatic or aromatic structure. 
Diols of from 2 to 15 carbon atoms are preferred. Examples are 
1,2-ethanediol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 
1,3-butanediol, 1,2-butanediol, 1,5-pentanediol, 
2,2-dimethyl-1,3-propanediol, 1,6-hexanediol and isomers thereof, 
decamethylenediol, the isomeric dihydroxycyclohexanes, resorcinol, 
hydroquinone and the various dihydroxynaphthalenes. Of these, especially 
aliphatic diols of 2 to 8, in particular from 2 to 4, carbon atoms are 
preferred (1,2-ethanediol, 1,3-propanediol, 1,4-butanediol). 
In some cases it may also be advantageous to use unsaturated diols, for 
example but-2-ene-1,4-diol, in particular mixed with the aforementioned 
saturated diols. Examples of polyether esters of such mixtures are 
revealed in EP-A-49 823. 
Finally, suitable diols also include diphenols such as 
4,4'-dihydroxybiphenyl, di(4-hydroxyphenyl)methane and 
2,2-di(4-hydroxyphenyl)propane (frequently also referred to as bisphenol 
A). 
Instead of the diols it is of course also possible to use their ester 
forming derivatives; in these cases, the molecular weight may of course 
also be more than 250, depending on the nature of the derivative, since 
the preferred molecular weight range (MW&lt;250) relates to the diols 
themselves. 
The dicarboxylic acids HOOC--R--COOH preferably have molecular weights of 
less than 300 and can be aromatic, aliphatic or cycloaliphatic. The 
dicarboxylic acids may also have substituents which do not interfere with 
the course of the polymerization reaction. 
Examples of aromatic dicarboxylic acids are terephthalic acid, isophthalic 
acid, substituted dicarboxylic acids of the formula 
##STR3## 
where A is a chemical bond, alkylene of 1 to 3 carbon atoms, --CO--, --S-- 
or --SO.sub.2 --, 1,5, 2,6- or 2,7-naphthalenedicarboxylic acid and the 
C.sub.1 -C.sub.6 -alkyl-substituted derivatives thereof. Of these, 
terephthalic acid, isophthalic acid, mixtures thereof or mixtures of 
terephthalic acid or isophthalic acid with other dicarboxylic acids are 
preferred. 
Examples of aliphatic dicarboxylic acids which can be used are oxalic acid, 
fumaric acid, maleic acid, citraconic acid, sebacic acid, adipic acid, 
glutaric acid, succinic acid and azelaic acid, to name but a few. 
It will be understood that it is also possible to use mixtures of various 
aliphatic dicarboxylic acids. As with the diols it is also possible to use 
instead of the acids themselves their ester-forming derivatives. This has 
in fact been found to be particularly advantageous in some cases. 
For further long-chain glycols HO--G--OH, short-chain diols HO--D--OH and 
dicarboxylic acids HOOC--R--COOH, reference is made to U.S. Pat. No. 
3,651,014. 
As mentioned earlier, the proportion of the long-chain segments is in 
general from 5 to 70% by weight, preferably from 7 to 50% by weight, and 
the proportion of short-chain segments is correspondingly from 30 to 95% 
by weight, preferably from 50 to 93% by weight. The weight proportion of 
each type of segment has a bearing inter alia on the hardness of the 
products. 
The dicarboxylic acids in the long-chain and short-chain segments can be 
identical or different; similarly, mixtures of diols or dicarboxylic acids 
can also be used in the preparation of the long-chain and short-chain 
segments. 
The above remarks indicate that a multiplicity of different segmented 
co(polyether ester)s can be used as component A). Of these, copolyether 
esters whose long-chain units are derived from poly(1,4-alkylene oxide) 
glycol having a molecular weight of from 600 to 2000, terephthalic acid 
and 1,4-butanediol are preferred. 
In some cases it has been found to be advantageous to replace some of the 
terephthalic acid by isophthalic acid, adipic acid or sebacic acid or some 
of the 1,4-butanediol by other diols, for example 1,3-propanediol, 
1,5-pentanediol or but-2-ene-1,4-diol. Such products are described in U.S. 
Pat. No. 3,651,014 and EP-A-49 823. 
Processes for preparing segmented co(polyether ester)s are known per se and 
described in the literature, making further comment superfluous. Reference 
may merely be made to U.S. Pat. Nos. 3,651,014, 3,784,520 and a review by 
G. K. Hoeschele (Chimia 28 (1974), 544). 
The co(polyether ester)s A) may contain stabilizers for protection against 
thermal or oxidative degradation, as described for example in U.S. Pat. 
Nos. 4,136,090 and 4 185 003 and in a paper by G. K. Hoeschele (Angew. 
Makromolekulare Chemie 58/59 (1977), 299-319). 
Component B) of the thermoplastic molding compositions of the present 
invention comprises customary additives and processing aids such as 
stabilizers, oxidation retardants, thermal stabilizers, UV absorbers, 
demolding agents, colorants such as dyes and pigments, fibrous and 
pulverulent fillers and reinforcing agents, nucleating agents, 
plasticizers, etc., the amount of which generally does not exceed 50% by 
weight. 
Examples of oxidation retardants and heat stabilizers are halides of metals 
of group I of the Periodic Table, for example sodium, potassium and/or 
lithium halides, alone or combined with copper(I) halides, for example 
chlorides, bromides, or iodides, sterically hindered phenols, 
hydroquinones, aromatic secondary amines such as diphenylamines, various 
substituted representatives of these groups and mixtures thereof, in 
concentrations of up to 1% by weight, based on the weight of the 
thermoplastic molding compositions. 
Suitable UV stabilizers, which in general are used in amounts of up to 2% 
by weight, based on the molding composition, are various substituted 
resorcinols, salicylates, benzotriazoles and benzophenones. 
It is also possible to add organic dyes such nigrosine, pigments such as 
titanium dioxide, cadmium sulfide, cadmium selenide, phthalocyanines, 
ultramarine blue and carbon black as colorants and also fibrous and 
pulverulent fillers and reinforcing agents. Examples of the latter are 
carbon fibers, glass fibers, amorphous silica, asbestos, calcium silicate 
(wollastonite), aluminum silicate, magnesium carbonate, kaolin, chalk, 
quartz powder, mica and feldspar. The proportion of such fillers and 
colorants is in general up to 50% by weight, preferably 20 to 35% by 
weight. 
The nucleating agents used can be for example chalk, calcium fluoride, 
sodium phenylphosphinate, alumina and finely divided 
polytetrafluoroethylene. 
Examples of plasticizers are dioctyl phthalate, dibenzyl phthalate, butyl 
benzyl phthalate, hydrocarbon oils, N-(n-butyl)benzenesulfonamide and o- 
and p-tolylethylsulfonamide. 
Other suitable additives are all flameproofing agents known for polyamides, 
in particular those based on phosphorus compounds or red phosphorus 
itself. 
Component C) of the thermoplastic molding compositions of the present 
invention comprises from 40 to 99.5% by weight, preferably from 92 to 99% 
by weight, in particular from 97.5 to 98.5% by weight, of a polyamide 
prepolymer having a viscosity number of from 40 to 80 ml/g, preferably 45 
to 65 ml/g, measured on a 0.5% strength by weight solution in concentrated 
sulfuric acid at 23.degree. C. 
Suitable polyamides which can be used for preparing component C) are 
thermoplastic partly crystalline polyamides. 
It is in particular also possible to use aromatic copolyamides which are 
partly crystalline and formed essentially from 
C.sub.1) 20-90% by weight of units derived from terephthalic acid and 
hexamethylenediamine, 
C.sub.2) 0-50% by weight of units derived from ,-caprolactam .epsilon.and 
C.sub.3) 0-80% by weight of units derived from adipic acid and 
hexamethylenediamine. 
The component C.sub.1) contains 20-90% by weight of units derived from 
terephthalic acid and hexamethylenediamine. A small proportion of the 
terephthalic acid, preferably not more than 10% by weight of the total 
aromatic dicarboxylic acids used, can be replaced with isophthalic acid or 
other aromatic dicarboxylic acids, preferably those in which the carboxyl 
groups are in the para position. 
As well as units derived from terephthalic acid and hexamethylenediamine, 
the copolyamides contain units derived from .epsilon.-caprolactam and/or 
units derived from adipic acid and hexamethylenediamine. 
The proportion of units derived from .epsilon.-caprolactam is not more than 
50% by weight, preferably from 20 to 50% by weight, in particular from 25 
to 40% by weight, while the proportion of units derived from adipic acid 
and hexamethylenediamine is up to 80% by weight, preferably from 30 to 75% 
by weight, in particular from 35 to 65% by weight. 
The copolyamides may also contain not only units of .epsilon.-caprolactam 
but also units of adipic acid and hexamethylenediamine; in this case, it 
is of advantage when the proportion of units which are free of aromatic 
groups is at least 10% by weight, preferably at least 20% by weight. The 
ratio of units derived from .epsilon.-caprolactam on the one hand and from 
adipic acid and hexamethylenediamine on the other is not subject to any 
special restriction.

Polyamides which are particularly advantageous for many purposes contain 
from 50 to 80, in particular from 60 to 75, % by weight of units derived 
from terephthalic acid and hexamethylenediamine (units C.sub.1)) and from 
20 to 50, preferably from 25 to 40, % by weight of units derived from 
.epsilon.-caprolactam (units C.sub.2)). 
As well as the above-described units C.sub.1) to C.sub.3), the partly 
aromatic copolyamides may contain minor amounts, preferably not more than 
15% by weight, in particular not more than 10% by weight, of further 
polyamide building blocks as known from other polyamides. These building 
blocks can be derived from dicarboxylic acids of from 4 to 16 carbon atoms 
and aliphatic or cycloaliphatic diamines of from 4 to 16 carbon atoms and 
also from aminocarboxylic acids or the corresponding lactams of from 7 to 
12 carbon atoms. Suitable monomers of this type are suberic acid, azelaic 
acid, sebacic acid and isophthalic acid as representatives of dicarboxylic 
acids, 1,4-butanediamine, 1,5-pentanediamine, piperazine, 
4,4'-diaminodicyclohexylmethane, 2,2-(4,4'-diaminodicyclohexyl)propane and 
3,3'-dimethyl-4,4'-diaminodicyclohexylmethane as representatives of 
diamines, and capryllactam, enantholactam, omega-aminoundecanoic acid and 
laurolactam as representatives of lactams and aminocarboxylic acids. 
Other particularly advantageous partly aromatic copolyamides are those 
whose triamine content is less than 0.5, preferably less than 0.3, % by 
weight. 
Partly aromatic copolyamides prepared by most existing processes (cf. U.S. 
Pat. No. 4,603,166) have triamine contents of above 0.5% by weight, which 
leads to a deterioration in product quality and to problems with 
continuous production. The triamine responsible for these problems is in 
particular dihexamethylenetriamine, formed from the hexamethylenediamine 
used in the preparation. 
Copolyamides of a low triamine content have for the same solution viscosity 
a lower melt viscosity than products of similar composition which have a 
higher triamine content. This improves not only the processing but also 
the product properties. 
The melting points of the partly aromatic copolyamides lie within the range 
from 260.degree. C. to above 300.degree. C., this high melting point also 
being associated with a high glass transition temperature of in general 
more than 75.degree. C., in particular more than 85.degree. C. (in the dry 
state). 
Binary copolyamides based on terephthalic acid, hexamethylenediamine and 
.epsilon.-caprolactam which contain about 70% by weight of units derived 
from terephthalic acid and hexamethylenediamine have melting points of the 
order of 300.degree. C. and (in the dry state) a glass transition 
temperature of more than 110.degree. C. 
Binary copolyamides based on terephthalic acid, adipic acid and 
hexamethylenediamine reach melting points of 300.degree. C. or more even 
at lower levels of about 55% by weight of units of terephthalic acid and 
hexamethylenediamine (HMD), although the glass transition temperature is 
not quite as high as in the case of binary copolyamides which contain 
.epsilon.-caprolactam instead of adipic acid or adipic acid/HMD. 
Further suitable polyamides can be prepared for example by condensation of 
equimolar amounts of saturated dicarboxylic acid of from 4 to 12 carbon 
atoms with a diamine of 4 to 14 carbon atoms or by condensation of 
.omega.-aminocarboxylic acids or polyaddition of lactams. 
Examples of polyamides are polyhexamethyleneadipamide, 
polyhexamethyleneazelamide, polyhexamethylenesebacamide, 
polyhexamethylenedodecanediamide, polytetramethyleneadipamide and the 
polyamides obtained by ring opening of lactams such as polycaprolactam and 
polylaurolactam. 
In general, these partly crystalline polyamides are linear. 
Particular preference is given to polytetramethyleneadipamide, 
polyhexamethyleneadipamide and copolyamides of terephthalic acid, 
hexamethylenediamine and .epsilon.-caprolactam where the 
.epsilon.-caprolactam content is less than 50% by weight, in particular 
polyhexamethyleneadipamide. However, it is also possible to use mixtures 
of different polyamides. 
The polyamide prepolymers having a viscosity number of from 40 to 80 ml/g 
(component C)) can be prepared by the processes described in EP-A-129 195 
and -129 196. 
In these processes, an aqueous solution of the monomers is heated under 
elevated pressure to 250.degree.-300.degree. C. with simultaneous 
evaporation of water and formation of a prepolymer, then prepolymer and 
steam are continuously separated, the steam is rectified and the entrained 
diamines are recycled. Finally, the prepolymer is passed into a 
polycondensation zone and polycondensed at from 250.degree. to 300.degree. 
C. under a superatmospheric pressure of from 1 to 10 bar. An essential 
requirement of the process is that the aqueous salt solution be heated 
under a superatmospheric pressure of from 1 to 10 bar within a residence 
time of less than 60 seconds, on exit from the vaporizer zone the degree 
of conversion being advantageously at least 93% and the water content of 
the prepolymer being not more than 7% by weight. 
These short residence times substantially prevent the formation of 
triamines. 
The aqueous solutions used generally have a monomer content of from 30 to 
70% by weight, in particular from 40 to 65% by weight. 
The aqueous salt solution is advantageously passed at from 50.degree. to 
100.degree. C. continuously into a vaporizer zone where the aqueous salt 
solution is heated to 250.degree.-330.degree. C. under a superatmospheric 
pressure of from 1 to 10, preferably from 2 to 6, bar. It will be 
understood that the temperature employed is above the melting point of the 
particular polyamide to be prepared. 
As mentioned earlier, it is essential that the residence time in the 
vaporizer zone is not more than 60 seconds, preferably from 10 to 55 
seconds, in particular from 10 to 40 seconds. 
The degree of conversion on exit from the vaporizer zone is not less than 
93%, preferably from 95 to 98%, and the water content is preferably within 
the range from 2 to 5, in particular from 1 to 3, % by weight. 
The vaporizer zone is advantageously constructed as a tube bundle. Of 
particular advantage are tube bundles in which the cross-section of the 
individual tubes periodically is recurringly tubular or slot-shaped. 
It has also been found to be advantageous to pass the mixture of 
prepolymers and steam as it emerges from the vaporizer zone and before 
phase separation has taken place through a tubular mass transfer zone 
which has been equipped with internal fitments. This zone is kept under 
the temperature and pressure conditions employed in the vaporizer zone. 
The internal fitments, for example packing such as Raschig rings, metal 
rings or in particular wire netting, constitute a large surface area. This 
ensures intimate contact between the phases, i.e. prepolymer and steam, 
and serves to considerably reduce the amount of diamine liberated with the 
steam. In general, a residence time of from 1 to 15 minutes is maintained 
in the mass transfer zone. The mass transfer zone is advantageously 
constructed as a tube bundle. 
The two-phase mixture of steam and prepolymer emerging from the vaporizer 
zone or the mass transfer zone is separated. Separation generally takes 
place automatically in a vessel due to the physical differences; the lower 
part of the vessel is advantageously constructed as a polymerization zone. 
The liberated vapors consist essentially of steam and diamines entrained 
in the course of the evaporation of the water. These vapors are passed 
into a column and rectified. Suitable columns are for example packed 
columns, bubble cap columns or sieve plate columns having from 5 to 15 
theoretical plates. The column is advantageously operated under the same 
pressure conditions as the vaporizer zone. The diamines present in the 
vapors are separated off in the course of the rectification and fed back 
into the vaporizer zone. It is also possible to feed the diamines into the 
downstream polymerization zone. The rectified steam obtained is taken off 
at the top of the column. 
The prepolymer obtained, which according to its degree of conversion 
consists essentially of low molecular weight polyamide with or without 
residues of unconverted salts, is passed into a polymerization zone. In 
the polymerization zone the resulting melt is polycondensed at from 
250.degree. to 330.degree. C., in particular at from 270.degree. to 
310.degree. C., under a superatmospheric pressure of from 1 to 10 bar, in 
particular from 2 to 6 bar. Advantageously, the vapors which are released 
here are rectified together with the abovementioned vapors in the column; 
preferably a residence time of from 5 to 30 minutes is maintained in the 
polycondensation zone. The polyamide prepolymer thus obtained, which 
generally has a viscosity number of from 40 to 80 ml/g, preferably from 45 
to 60 ml/g, measured on a 0.5% strength by weight solution in 96% strength 
sulfuric acid at 23.degree. C., is removed continuously from the 
condensation zone. 
In a preferred process, the polyamide prepolymer thus obtained is passed as 
a molten liquid through a discharge zone with simultaneous removal of the 
residual water present in the melt. Suitable discharge zones are for 
example devolatilization extruders. The melt thus freed of water is then 
cast in strand form and granulated. The granules obtained (component C)) 
are melted at about 20.degree. C. above the melting point of component C) 
(at about 280.degree. C. in the case of polyhexamethyleneadipamide), 
preferably in a twin-screw extruder, and mixed with the thermoplastic 
polyester elastomer (component A)) and with or without component B), and 
the mixture is extruded in strand form, cooled and granulated. 
In a particularly preferred embodiment, it is also possible to add 
component A) and any B), if used, straight away to the devolatilization 
extruder, in which case the devolatilization extruder is customarily 
equipped with suitable mixing elements, such as kneaders. The mixture is 
then likewise extruded in strand form, cooled and granulated. 
These granules are condensed in solid phase under an inert gas atmosphere 
at a temperature below the melting point, for example from 170.degree. to 
240.degree. C., to the desired viscosity in a continuous or batchwise 
manner. The batchwise solid phase condensation can be carried out for 
example in tumble dryers, while the continuous solid phase condensation 
can be carried out in heat treatment tubes through which a hot inert gas 
flows. Preference is given to the continuous solid phase condensation, the 
inert gas used being nitrogen or superheated steam, advantageously steam 
obtained at the top of the column. 
Following the postcondensation in solid phase the viscosity number, 
measured on a 0.5% strength by weight solution in 96% strength sulfuric 
acid at 23.degree. C., is in general within the range from 120 to 500 
ml/g, preferably from 130 to 200 ml/g. 
The thermoplastic molding compositions of the present invention are notable 
for a balanced range of properties, in particular for good flowability and 
flame resistance. They are suitable for producing fibers, films and 
moldings. 
EXAMPLES 
Component A 
A block polyether-ester composed essentially of units derived from 
poly(1,4-butylene glycol), terephthalic acid and 1,4-butanediol, having a 
Shore hardness of 92 A or 40 D (according to ASTM D-2240) and a melt flow 
index of from 4 to 6.5 g/10 min (190.degree. C., 2.16 kg load) 
(Hytrel.RTM. 4056 from DuPont de Nemours and Company). 
Component C 
A polyamide prepolymer prepared by the process described in EP-A-129 195 by 
dissolving 669.6 kg of an equipmolar adipic acid/hexamethylenediamine salt 
at 80.degree. C. in 330.4 kg of water and continuously polycondensing in a 
tube bundle reactor at 283.degree. C. and 2.8 bar with a throughput 
corresponding to a polyamide rate of 50 kg/h. The product has a viscosity 
number of 58 ml/g, measured on a 0.5% strength by weight solution in 
concentrated sulfuric acid at 23.degree. C. 
EXAMPLES 1 TO 3 
The polyamide prepolymer (component C) was screw discharged in melt form 
from the separation vessel of the polycondensation plant into a twin-screw 
extruder (ZSK 53 from Werner & Pfleiderer) and mixed with component A at 
280.degree. C. and 100 rpm. A vacuum was then applied for devolatilization 
in the course of which virtually no postcondensation occurred. The product 
was extruded in strand form, cooled, granulated and postcondensed with 
superheated steam at 182.degree. C. in the course of a residence time of 
11 hours. The viscosity number was 140 ml/g, measured on a 0.5% strength 
by weight solution in concentrated sulfuric acid at 23.degree. C. 
Comparative Examples C1 TO C3 
Examples 1 to 3 were repeated, except that component A was replaced by 
other additives. 
Comparative Example C1 
Aluminum tristearate (Alugel.RTM. from Barlocher, Munich) was incorporated. 
Comparative Example C2 
An ethylene/n-butyl acrylate/acrylic acid copolymer having a weight ratio 
of ethylene:n-butyl acrylate:acrylic acid of 82:3:5 and a melt flow index 
MFI of 10.5 g/10 min (at 190.degree. C. under a load of 2.16 kg) was 
incorporated. 
Comparative Example C3 
An ethylene/propylene rubber (weight ratio ethylene:propylene of 45:55), 
grafted with 1% by weight of maleic anhydride, having a melt flow index 
MFI of 150 g/10 min (at 23.degree. C. under a load of 21.6 kg) 
(Exxelor.RTM. 1803 from Exxon Chemical) was incorporated. 
Comparative Example C4 
The procedure of Examples 1 to 3 was repeated, except that no component A 
was used. 
Comparative Examples C5 TO C7 
Component C* 
A polyamide consisting of units derived from hexamethylenediamine and 
adipic acid and having a viscosity number of 145 ml/g (measured on a 0.5% 
strength by weight solution in concentrated sulfuric acid at 23.degree. 
C.) (Ultramid.RTM. A3 from BASF AG). 
The polyamide (component C*) was mixed in granule form with component A 
(C5) and aluminum tristearate (Alugel.RTM. from Barlocher, Munich) (C7) or 
aluminum tristearate (C6) in a twin-screw extruder (ZSK 53 from Werner & 
Pfleiderer) at 280.degree. C., extruded in strand form, cooled and 
granulated. 
The products were measured in respect of the modulus of elasticity in 
accordance with DIN 54 457, the tensile strength in accordance with DIN 54 
455 and the melt flow index MFI in accordance with DIN 53 735 (at 
285.degree. C. under a load of 5 kg). The penetration energy W.sub.tot was 
determined in accordance with DIN 53 443 at 23.degree. C. on 2 mm thick 
round disks 60 mm in diameter injection molded at 280.degree. C. A test 
mold for vacuum cleaner lids was used to determine the fastest possible 
cycle time at 280.degree. C. The burning test was carried out in 
accordance with UL94 (ANSI) on flat bars having the thicknesses 0.8 mm/1.6 
mm/3.2 mm. 
The compositions and properties are summarized in the Table. 
TABLE 
__________________________________________________________________________ 
Modulus of 
Tensile Cycle 
Ex- Composition [% by wt] 
elasticity 
strength 
W.sub.tot 
Burning 
time 
MFI 
ample 
A) 
C) C*) 
Additives 
[kJ/m.sup.2 ] 
[kJ/m.sup.2 ] 
[J/m] 
test [sec] 
[g/10 min] 
__________________________________________________________________________ 
.sup. 1 
1 99.0 
-- -- 3031 85 104 V2/V2/V- 
31 138 
.sup. 2 
2 98.0 
-- -- 2946 83 111 V2/V2/V2 
24 140 
.sup. 3 
4 96.0 
-- -- 2888 81 120 V2/V2/V2 
24 155 
C1 -- 
99.3 
-- 0.7 Aluminum 
3010 86 30 V-/V-/V- 
44 105 
tristearate 
C2 -- 
98.0 
-- 2.0 Ethylene/ 
2900 82 140 V-/V-/V- 
46 98 
n-butyl acrylate/ 
acrylic acid 
copolmyer 
C3 -- 
98.0 
-- 2.0 Graft rubber 
2895 81 140 V-/V-/V- 
44 101 
C4 -- 
100.0 
-- -- 3025 85 102 V2/V2/V2 
40 109 
C5 2 -- 98.0 
-- 2910 84 90 V-/V-/V- 
26 133 
C6 -- 
-- 99.3 
0.7 Aluminum 
3025 86 38 V2/V2/V2 
28 160 
tristearate 
C7 2 -- 97.3 
0.7 Aluminum 
2955 82 45 V2/V2/V2 
26 142 
tristearate 
__________________________________________________________________________