High-molecular, segmented, thermoplastically processable, aromatic polycarbonates containing co-condensed dimeric fatty acid esters, their preparation and their use

The present invention relates to polycarbonate compounds characterized in that dimeric fatty acid ester soft segments are co-condensed therein. The invention further relates to processes for preparation of these compounds and their use in films and molded articles.

SUMMARY OF THE INVENTION 
The present invention relates to high-molecular, segmented, 
thermoplastically processable aromatic-polycarbonates characterized by its 
co-condensed dimeric fatty acid ester segments having an average molecular 
weight Mn (number-average) between 800 and 20,000 and to a process for 
their preparation. 
BACKGROUND OF THE INVENTION 
Thermoplastically processable, high-molecular, segmented, aromatic 
polycarbonate elastomers containing a variety of soft segments and their 
preparation processes are known (see, for example, U.S. Pat. No. 
3,161,615, U.S. Pat. No. 3,030,335, U.S. Pat. No. 3,287,442, U.S. Pat. No. 
3,189,662, U.S. Pat. No. 3,169,121, German Auslegeschrift 1,162,559, 
German Offenlegungsschrift 2,411,123, German Offenlegungsschrift 
2,636,783, German Offenlegungsschrift 2,702,626, German 
Offenlegungsschrift 2,636,784, German Offenlegungsschrift 2,726,416, 
German Offenlegungsschrift 2,726,376, German Offenlegungsschrift 
2,726,417, and German Patent Application P 28 27 325. 
The products are thermoplastically processable and, because of their soft 
segments such as aliphatic polyethers, aliphatic polyesters, aliphatic 
polycarbonates or polysiloxanes, are characterized by their elasticity. 
The elasticity of these products depends on the ratio between the aromatic 
polycarbonate hard segments and the aliphatic soft segments such that the 
elasticity and elongation at break increase with the proportion of soft 
segment increase. These products also have a high heat distortion 
temperature resulting from the crystalline aromatic polycarbonate regions 
which impart to the polymer a high cross-linking density, even at 
relatively high temperatures. In addition, these polycarbonate elastomers 
can also be used to obtain products with a comparatively low heat 
distortion point resulting from a clear amorphous phase separation of the 
hard segment from the soft segment. 
The disadvantage of almost all these products is that the aromatic 
polycarbonate hard segments, which impart to the polymer the high heat 
distortion temperature, do not form a separate phase sufficiently rapidly 
after thermoplastic processing and the products thus tend to stick to one 
another; the tackiness can be eliminated by additional processing steps 
such as, by subjecting the products to a heat treatment or to a drawing 
and a heat treatment after the thermoplastic processing. There is 
therefore a considerable expenditure of effort and expense associated with 
freeing these products from tackiness. 
It has now been found, surprisingly, that aromatic polycarbonate elastomers 
which contain at least 5% by weight of co-condensed dimeric fatty acid 
esters as soft segments are no longer tacky after thermoplastic 
processing. It is particularly surprising that these products feature 
separate phases immediately after thermoplastic processing and are 
flexible also at low temperatures. Such controlled phase separation 
between the aromatic polycarbonate segments, based, for example, on 
bisphenol-A polycarbonate, and the polyester segment based on 
hexane-1,6-diol and dimeric fatty acid, while transparency is retained was 
hitherto unknown. 
The preparation of polyester-polycarbonates from dimeric fatty acid, 
bisphenol A and phosgene by the pyridine process is in itself known and is 
described in U.S. Pat. No. 3,169,121, Example 17. The products according 
to that patent are built up only from dimeric fatty acid blocks with 
molecular weights of 560. In contrast, the polycarbonates, with 
co-condensed dimeric fatty acid esters, according to the present invention 
contain polyester blocks having molecular weights (number-average)Mn of 
800 to 20,000, preferably 1,000 to 15,000 and in particular 2,000 to 
10,000, and diols and are characterized by their separate phases. It is 
this critical feature which enables their use according to the invention. 
The polycarbonates according to the invention containing at least 5% by 
weight of co-condensed dimeric fatty acid esters can be processed 
thermoplastically into transparent films, from which bags for packaging 
biological liquids and parenteral agents can be produced by heat impulse 
welding. These bags have a sufficiently high heat distortion temperature 
that they can be sterilized with steam in an autoclave at 121.degree. C. 
DETAILED DESCRIPTION OF THE INVENTION 
All diphenols are suitable for the preparation of the high-molecular 
polycarbonate elastomers according to the invention, examples being 
hydroquinone, resorcinol, dihydroxydiphenyls, bis-(hydroxyphenyl)-alkanes, 
bis-(hydroxyphenyl)-cycloalkanes, bis-(hydroxyphenyl)-sulphides, 
bis-(hydroxyphenyl)-ethers, bis-(hydroxyphenyl)-sulphoxides, 
bis-(hydroxyphenyl)-sulphones and 
.alpha.,.alpha.-bis-(hydroxyphenyl)-diisopropylbenzenes, and 
nuclear-alkylated and nuclear-halogenated derivatives thereof. These and 
other suitable aromatic dihydroxy compounds are listed, for example, in 
U.S. Pat. Nos. 3,271,367 and 2,999,846, and in German 
Offenlegungsschriften 2,063,050 and 2,211,957. 
Diphenols which can be employed according to the invention are, in 
particular, those of the formula (I) 
##STR1## 
wherein X denotes a single bond, --CH.sub.2 --, 
##STR2## 
and O, S, SO.sub.2 or 
##STR3## 
Y.sub.1 to Y.sub.4 are identical or different and denote hydrogen, C.sub.1 
-C.sub.4 -alkyl, preferably methyl, or halogen, preferably chlorine or 
bromine. 
Examples of suitable diphenols are 4,4'-dihydroxydiphenyl, 
2,2-bis-(4-hydroxyphenyl)-propane, 
2,4-bis-(4-hydroxyphenyl)-2-methylbutane, 
1,1-bis-(4-hydroxyphenyl)-cyclohexane, 
.alpha.,.alpha.-bis-(4-hydroxyphenyl)-p-diisopropylbenzene, 
2,2-bis-(3-methyl-4-hydroxyphenyl)-propane, 
2,2-bis-(3-chloro-4-hydroxyphenyl)-propane, 
bis-(3,5-dimethyl-4-hydroxyphenyl)-methane, 
2,2-bis-(3,5-dimethyl-4-hydroxyphenyl)-propane, 
bis-(3,5-dimethyl-4-hydroxyphenyl)-sulphone, 
2,4-bis-(3,5-dimethyl-4-hydroxyphenyl)2-methylbutane, 
1,1-bis-(3,5-dimethyl-4-hydroxyphenyl)cyclohexane, 
.alpha.,.alpha.'-bis-(3,5-dimethyl-4-hydroxyphenyl)-p-diisopropylbenzene, 
2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane and 
2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane. 
Preferred diphenols are, for example, 2,2-bis-(4-hydroxyphenyl)-propane, 
1,1-bis-(4-hydroxyphenyl)-cyclohexane, 
2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane, 
2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane, 
2,2-bis-(3,5-dimethyl-4-hydroxyphenyl)-propane, 
bis-(3,5-dimethyl-4-hydroxyphenyl)-methane and 
bis-(4-hydroxyphenyl)-sulphide. 
It is possible to use either one or a mixture of several of the suitable 
diphenols. 
In addition to the aromatic diphenols, known branching agents with three or 
more functional groups, in particular those with three or more phenolic 
hydroxyl groups, can be used in the preparation of the polycarbonates of 
the invention. The amount of the branching agent added is kept within the 
amounts known as customary, i.e. between 0.05 and 2 mol %, relative to 
incorporated diphenols. The preparation of branched polycarbonates is 
described, for example in German Offenlegungsschrift 1,570,533 and German 
Offenlegungsschrift 1,595,762, and in U.S. Pat. No. 3,544,514 and U.S. 
Pat. No. Re. 27,682, all incorporated herein by reference. 
Phenols such as p-tert.-butylphenol, p-chlorophenol, 2,4,6-tribromophenol 
and phenol, can be employed as chain stoppers in the customary amounts, 
which are determined by the particular molecular weight to be established 
in the polycarbonate elastomers according to the invention. 
Dimeric fatty acid esters which are suitable as segments according to the 
invention are polyesters which contain aliphatic hydroxyl end groups or 
aliphatic carboxyl end groups and are obtainable from reacting a dimeric 
fatty acid having a molecular weight (number-average) Mn of about 300 to 
800, preferably 500 to 600, and a diol. The polyesters can be obtained in 
known manners, for example in the presence of esterification catalysts, at 
temperatures between 150.degree. and 200.degree. and at reaction times 
between 20 and 50 hours. The polyesters containing hydroxyl end groups are 
obtainable by using an excess amount of diol, relative to the dimeric 
fatty acid and the polyesters containing carboxyl end groups are 
obtainable by using an excess of dimeric fatty acid relative to the diol. 
The dimeric fatty acid esters which are suitable according to the 
invention have average molecular weights (number-average) Mn of 800 to 
20,000 preferably of 1,000 to 15,000 and in particular of 2,000 to 10,000. 
The molecular weight required for the dimeric fatty acid ester is in each 
case controlled in a known manner by the selected ratio between the diol 
and dimeric fatty acid. 
By dimeric fatty acid there is to be understood the dimerization product of 
unsaturated fatty acids (C.sub.18) such as oleic acid, linoleic acid and 
linolenic acid. The preparation and structure of the dimerized fatty acid 
is described in J. Am. Chem. Soc. 66, 84 (1944) and in U.S. Pat. No. 
2,347,562. Commercially available dimeric fatty acids of various 
qualities, which differ from each other with respect to the degree of 
unsaturation and to the monomer and trimer content, may be used. The 
preferred commercially available dimeric fatty acid compositions are those 
that are virtually free from monomer and trimer fractions and are 
completely saturated. A hydrogenated dimeric fatty acid which is prepared, 
for example, by dimerizing oleic acid and then hydrogenating the product 
is preferably suitable. Mixtures of dimeric fatty acids and trimeric fatty 
acids can also be used for this application. 
Examples of possible dihydric alcohols are, optionally as mixtures with one 
another, ethylene glycol, 1,2- and 1,3-propylene glycol, 1,2-, 2,3-, 1,3- 
and 1,4-butanediol, pentanediols, neopentylglycol, hexanediols, for 
example, 1,6-hexanediol, trimethylhexanediols, 1,8-octanediols, 
decanediols, dodecanediols, octadecanediols, 
2,2-dimethyl-propane-1,3-diol, 2,2-dimethyl-3-hydroxypropionate, 
diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene 
glycol, tripropylene glycol, tetrapropylene glycol, 
1,4-cyclohexanedimethanol, 1,1-cyclohexanedimethanol and 
perhydrobisphenols, for example 4,4'-(1-methylethylidene)-bis-cyclohexanol 
and 2,2-bis-(4-(2-hydroxyethoxy)-phenyl)-propane. 
Polyhydric alcohols can also be used, such as, for example, glycerol, 
1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 
trimethylolbutane, pentaerythritol, tetroses, di- and tri-methylolpropane, 
pentoses, 2,2,6,6-tetrakis-(hydroxymethyl)-cyclohexane, hexoses, 
di-pentaerythritol and tri-pentaerythritol. It is furthermore possible to 
use ethylene oxide adducts or propylene oxide adducts of such polyols, as 
long as the average number of carbon atoms per molecule does not exceed 
60, and polyethylene glycols, polypropylene glycols and polybutylene 
glycols. 
The dimeric fatty acid esters which are suitable according to the invention 
and contain carboxyl end groups can be used as such in the preparation of 
polycarbonates, by the known solution process, that is to say, for 
example, by the phase boundary process (in this context, see German 
Offenlegungsschrift 2,636,783 or by the so-called "pyridine process". 
The dimeric fatty acid esters which are suitable according to the invention 
and contain hydroxyl end groups can be used directly as such only for the 
preparation of polycarbonates by the "pyridine process" (see, for example, 
Journal of Polymer Science Part e, Polymer Symposia No. 4, 1963, Part 1, 
pages 707 to 730). To prepare polycarbonates by the phase boundary 
process, the dimeric fatty acid esters containing hydroxyl end groups must 
be converted either into dimeric fatty acid esters containing hydroxyaryl 
carbonate end groups (in this context, see, for example German 
Offenlegungsschrift 2,726,376 and German Patent Applications P 28 27 325 
and P 28 27 526), or into the corresponding bischlorocarbonic acid esters 
(in this context, see, for example, German Auslegeschrift 1,162,559). The 
dimeric fatty acid esters containing hydroxyaryl carbonate end groups or 
chlorocarbonic acid ester end groups can, of course, be also used for the 
preparation of polycarbonates by the "pyridine process". 
The corresponding carboxylic acid halides, in particular carboxylic acid 
chlorides, of the dimeric fatty acid esters which are suitable according 
to the invention and contain carboxyl end groups can also be used for the 
preparation, according to the invention, of the polycarbonates according 
to the invention. 
The dimeric fatty acid esters containing carboxyl end groups can be 
converted into the corresponding carboxylic acid chlorides by the 
customary agents, such as, for example, thionyl chloride, PCl.sub.3, 
PCl.sub.5 and the like, in a known manner (in this context, see 
"Organikum" VEB Deutscher Verlag der Wissenschaften, Berlin 1967, 7th 
Edition, pages 466 to 467). 
Examples of dimeric fatty acid esters which are suitable according to the 
invention and contain hydroxyaryl carbonate end groups are those of the 
following ideal formulae (II to (IIi) 
##STR4## 
wherein --O--A--O-- is the bivalent diolate radical of a dimeric fatty 
acid ester which is suitable according to the invention, contains 
aliphatic hydroxyl end groups and has a Mn (number-average) of 800 to 
20,000, preferably 1,000 to 15,000 and in particular 2,000 to 10,000, 
and wherein, in formula (II), 
X and Y.sub.1 to Y.sub.4 are as defined for formula (I). 
Suitable hydroxyaryl carbonate terminated fatty acid esters which contain 
aliphatic carbonate groups also include those which are obtained by 
including aliphatic hydroxyl terminated fatty acid esters of the type 
described hereinabove as an additional reactant in the process described 
in Offenlegungsschrift 2,827,325. This published German Patent Application 
teaches the reaction of dihydric alcohols, bisphenols and diphenyl 
carbonate to yield aliphatic hydroxyaryl terminated polycarbonates 
suitable as precursors for the preparation of high molecular weight 
polycarbonate. 
The preparation of the polycarbonates according to the invention can 
essentially be carried out by the two known processes described briefly 
below (compare H. Schnell, "Chemistry and Physics of Polycarbonates," 
Polymer Rev., Volume IX, pages 27 et seq., Interscience Publishers). 
1. Preparation of a polycarbonate according to the invention in a 
heterogeneous phase system (phase boundary process). 
In this process, diphenols are dissolved in an aqueous alkaline phase, 
together, if appropriate, with monophenolic chain stoppers and with 
trifunctional or tetrafunctional branching agents. After adding the 
dimeric fatty acid ester, containing aliphatic carboxyl end groups or 
hydroxyaryl carbonate end groups, in a solvent suitable for the 
polycarbonate, a two-phase mixture is formed, into which phosgene is 
passed at 0.degree. C. to 60.degree. C. After adding a catalyst, 
high-molecular-weight weight polycarbonates containing co-condensed 
dimeric fatty acid esters are obtained. The mixture is worked up by 
separating off the organic phase and washing it until neutral and then 
distilling off the solvent, for example in twin-screw evaporation 
extruders at temperatures of 200.degree. to 250.degree.. 
Organic solvents which are suitable for the preparation of the 
polycarbonates according to the invention are the known solvents for 
thermoplastic polycarbonates, such as, for example, methylene chloride and 
chlorobenzene. 
Basic compounds which are suitable for the preparation of the aqueous 
alkaline phase are LiOH, NaOH, KOH, Ca(OH).sub.2 and/or Ba(OH).sub.2. 
Catalysts which are suitable for the polycondensation reaction are the 
tertiary aliphatic amine catalysts known for polycarbonate synthesis, such 
as trimethylamine, triethylamine, n-tripropylamine, n-tributylamine or 
N-ethylpiperidine. If appropriate, the known quaternary ammonium salts, 
such as, for example, tetrabutylammonium bromide, can also be used. 
The amount of catalyst used depends on the diphenol employed, while 
generally from 0.2 to 5 mol % are sufficient, when tetramethyl-substituted 
diphenols are used, 5 to 10 mol % are required. The amounts in each case 
are relative to the total amount of diphenols used in the total aromatic 
polycarbonate content in the polycarbonate elastomers. 
The amounts of organic phase are selected such that the reaction is carried 
out in a 5 to 20 percent strength organic solution, preferably in a 10 to 
15 percent strength organic solution. 
While the volume of aqueous alkaline phase is preferably equal to the 
overall volume of organic phase, it can also be larger or smaller than 
that volume. 
The pH value of the aqueous phase during the reaction is between 9 and 14, 
preferably between 12 and 13. 
2. Preparation of a polycarbonate according to the invention in a 
homogeneous phase system (pyridine process). 
In this process diphenols and the dimeric fatty acid esters which are 
suitable according to the invention, if appropriate together with 
trifunctional or tetrafunctional branching agents, are dissolved in an 
organic base, such as, for example, pyridine, into which methylene 
chloride is optionally admixed. After adding a suitable solvent for the 
polycarbonates formed, phosgene is passed into the mixture at a 
temperature between 0.degree. C. and 60.degree. C. The pyridine 
hydrochloride which forms during the reaction is filtered off and the 
organic phase is washed with dilute aqueous HCl, and then with water to 
neutrality. The organic solution of the polycarbonate is worked up as in 
the process described under 1. 
In addition to pyridine, organic bases which are suitable are 
triethylamine, dimethylaniline and tributylamine. Solvents for the 
polycarbonate according to the invention are those listed for the process 
described under 1. 
The amounts of organic phase are chosen such that the reactions can be 
carried out in an approximately 5 to 20 percent strength solution. 
The amounts of organic bases are chosen such than more than 2 mols of amine 
are used per mol of diphenol or phosgene employed. 
The particular ratios between the diphenol and the dimeric fatty acid 
esters which can be used according to the invention depend on the desired 
content of "soft segment" (dimeric fatty acid ester units) and that of the 
"hard segment" (aromatic carbonate units). 
Carbonate sources for the preparation, according to the invention, of the 
polycarbonates are carbonic acid halides, in particular carbonic acid 
chlorides, such as, for example, phosgene and COBr.sub.2, or 
bischlorocarbonic acid esters of the diphenols. The amount used is in each 
case less than 1/2 mol of diphenol per halogeno-carbonic acid group. 
The polycarbonates according to the invention consist of aromatic 
polycarbonate portions and dimeric fatty acid ester segments. The hardness 
and heat distortion temperature of the polycondensates increase and the 
elasticity and elongation at break decrease as the content of the aromatic 
polycarbonate increases. 
The polycarbonates according to the invention which contain more than about 
5% by weight of co-condensed dimeric fatty acid ester segments can also be 
termed polycarbonate elastomers. Their aromatic polycarbonate content is 
to be understood as the amount by weight of aromatic carbonate structural 
units of the following formula (III) 
##STR5## 
wherein D represents the diphenolate radicals in the polycarbonate 
elastomer, 
and in particular, of aromatic carbonate structural units of the formula 
(IV) 
##STR6## 
wherein X and Y.sub.1 to Y.sub.4 have the meaning given in the case of the 
formula (I). 
The soft segment content of the high-molecular polycarbonate elastomers 
according to the invention is to be understood as the amount by weight of 
the aliphatic carbonate structural units represented by (V) or carboxylate 
structural units represented by (VI) 
##STR7## 
wherein --O--A--O-- denotes the bivalent diolate radical as defined in 
formula (II) and 
##STR8## 
is the bivalent dicarboxylate radical of the dimeric fatty acid esters 
which are suitable according to the invention and contain aliphatic 
carboxyl end groups and have a Mn (number-average) of 800 to 20,000, 
preferably 1,000 to 15,000 and in particular 2,000 to 10,000. 
The present invention thus preferably relates to high-molecular, segmented, 
thermoplastically processable, aromatic polycarbonates based on 
co-condensed dimeric fatty acid ester segments which consist of about 30 
to 99 percent by weight, of aromatic carbonate structural units of formula 
(IV) and of 70 to 1 percent by weight of dimeric fatty acid ester segments 
of formula (V) or of formula (VI). 
A particular relation, that of 30 to 95 percent by weight, preferably 35 to 
80 percent by weight of formula (IV) and 70 to 5 and preferably 65 to 20 
percent by weight of formula (V) or of formula (VI) is preferred. Further 
preferred is an embodiment consisting of 95.1 to 99 percent by weight, 
most preferred 90 to 99 percent by weight, of formula (IV) and 4.9 to 1 
percent by weight, and most preferred 4 to 1 percent by weight of formula 
(V) or of formula (VI). 
In addition to a particularly good thermal stability, the high-molecular, 
segmented thermoplastically processable polycarbonates according to the 
invention exhibit good transparency and, in proportion to the content of 
soft segment, high elasticity. 
The high-molecular polycarbonates according to the invention should have 
average molecular weights Mw (weight-average) of 25,000 to 200,000, 
preferably of 40,000 to 150,000, determined by the light scattering method 
with a dispersion photometer. The relative solution viscosities 
.eta..sub.rel (measured on solutions of 0.5 g of polycarbonate in 100 ml 
of CH.sub.2 Cl.sub.2 at 25.degree. C.) of the high-molecular 
polycarbonates according to the invention are between 1,2 and 3, 
preferably between 1,25 and 3, especially between 1,4 and 2,6. 
In addition to the dimeric fatty acid esters which are suitable according 
to the invention, other "soft segments" which are capable of being 
incorporated can be used for the preparation of the polycarbonates 
according to the invention. Examples of such soft segments are those which 
are already used and are based on polyethers, polyesters, polyacetals and 
polythioethers, in German Patent Application P 28 37 526, or based on 
aliphatic polycarbonates, in German Patent Application P 28 27 325, or 
obtained from polysiloxanes, in accordance with U.S. Pat. No. 3,189,662 
and German Offenlegungsschrift 2,411,123, or from C--C linked polymers, in 
accordance with German Offenlegungsschrift 2,702,626. Such polycarbonate 
elastomers of the prior art can be substantially improved, in terms of 
phase separation and reduced tendency to tackiness, by co-condensing small 
amounts of the dimeric fatty acid ester soft segments according to the 
invention. 
The polycarbonates according to the invention can also be admixed with 
high-molecular polycarbonate elastomers based on polyethers, polyesters, 
polysiloxanes, polythioethers, polyacetals, aliphatic polycarbonates and 
C--C linked polymers, resulting in an improvement in their properties, 
such as, for example, phase separation and reduced tackiness. 
The polycarbonates according to the invention can furthermore also be 
admixed with other thermoplasts, for example bisphenol-A polycarbonates. 
Such polycarbonates, suitable as components, have preferably an 
.eta..sub.rel. (determined at 20.degree. C. in CH.sub.2 Cl.sub.2, c=0.5 
g/l) between about 1,2 and 1,45 and can have been made in known manner 
besides from the already mentioned 2,2-Bis-(4-hydroxyphenyl)-propane also 
from the other diphenols of formula (I). 
In addition to being used as packaging materials for biological liquids and 
parenteral agents, the polycarbonate elastomers according to the invention 
containing at least 5% by weight of co-condensed dimeric fatty acid esters 
as the soft segments can advantageously be used in all cases where a 
combination of hardness and elasticity, in particular low temperature 
flexibility, is desired, for example in bodywork construction, for the 
production of low-pressure tires for vehicles, for sheathings for tubes, 
sheets and pipes and for flexible disc pulleys. 
The packaging materials are produced from the polycarbonate elastomers 
which are suitable according to the invention and contain at least 5% by 
weight of co-condensed dimeric fatty acid esters as the soft segments by 
known processing methods for thermoplastic polymers, for example by the 
extrusion process under customary processing conditions. 
Extruded films can be processed to flexible bags by heat-sealing, heat 
impulse welding, ultrasonic welding or high frequency welding. After 
filling and steam sterilization, these bags pass the necessary drop tests. 
Extruded flat films of the material according to the invention have very 
good optical properties (light transmission: 90%, turbidity:2%), excellent 
mechanical properties (tensile strength: about 20 MPa, elongation at 
break: about 700%) and low temperature flexibility and an extremely low 
content of extractable constituents. 
The polycarbonates according to the invention containing less than about 5% 
by weight of co-condensed dimeric fatty acid esters can be used for 
applications for which customary thermoplastic polycarbonates are used, 
for example as films and sheets in the electrical industry. Such 
manufactured parts can be produced by the extrusion and injection-molding 
processes suitable for aromatic polycarbonates. 
Compared with comparable thermoplastic polycarbonates without co-condensed 
dimeric fatty acid esters, the polycarbonates according to the invention 
containing less than about 5% by weight of co-condensed dimeric fatty acid 
esters have the advantages of having a higher 
low-temperature-impact-strength and of being released from the mold more 
easily after thermoplastic processing. 
The polycarbonates according to the invention containing co-condensed 
dimeric fatty acid esters and between about 30% by weight and 99% by 
weight of aromatic carbonate structural units can be mixed with suitable 
additives customary in the technology of thermoplastic polyesters and of 
aromatic, thermoplastic polycarbonates, such as, for example, carbon 
black, kieselguhr, kaolin, clays, CaF.sub.2, CaCO.sub.3, aluminum oxides 
and customary glass fibers, in amounts of 2 to 4% by weight, in each case 
relative to the total weight of the molding composition, and with 
inorganic pigments, both as fillers and as nucleating agents. 
The stability of the aromatic polycarbonates according to the invention 
containing co-condensed dimeric fatty acid esters to UV light and 
hydrolysis can be improved by UV stabilizers, such as, for example, 
substituted "benzophenones" or "benztriazoles", in amounts customary for 
thermoplastic polyesters and aromatic polycarbonates, by hydrolysis 
stabilizers, such as, for example, monocarbodiimides and, mostly, 
polycarbodiimides (compare W. Neumann, J. Peter, H. Holtschmidt and W. 
Kallert, Proceeding of the 4th Rubber Technology Conference, London, 
22nd-25th May 1962, pages 738-751), in amounts of 0.2-5% by weight, 
relative to the total weight of the molding composition, and by the 
antiaging agents and stabilizers known in the chemistry of thermoplastic 
polyesters and of aromatic, thermoplastic polycarbonates. 
If flame-resistant molding compositions are desired, about 5 to 15% by 
weight, in each case relative to the weight of aromatic polycarbonates 
containing dimeric fatty acid esters, of flameproofing agents known in the 
chemistry of thermoplastic polyesters and of aromatic, thermoplastic 
polycarbonates, such as, for example, antimony trioxide tetrabromophthalic 
anhydride, hexabromocyclododecane, tetrachloro- or tetrabromo- 
bisphenol-A, tris-(2,3-dichloropropyl) phosphate or tetrachloro- or 
tetrabromo-phthalimides can be admixed to the polycarbonates, the 
tetrachloro- and tetrabromo- bisphenols statistically co-condensed in the 
polycarbonate portions of the aromatic polycarbonates according to the 
invention likewise exhibit flame-resistant properties. 
Processing auxiliaries, such as mold-release agents, known in the chemistry 
of thermoplastic polyesters and of thermoplastic, aromatic polycarbonates 
can also be used effectively. 
The average molecular weights given in the examples which follow are 
number-average (Mn) and are established by determining the OH number and 
the acid number. 
The viscosity of the prepolymer soft segments of Examples A and B is 
determined at 20.degree. in a flow cup 4 DIN 53 211 from Messrs. Erichsen. 
The relative solution viscosity .eta..sub.rel of Examples C 1-9 is defined 
as the viscosity of 0.5 g of the high-molecular polycarbonate in 100 ml of 
methylene chloride at 25.degree.. 
Investigations by gel chromatography were carried out at room temperature 
in tetrahydrofurane using Styragel columns (separation range: 
1.5.times.10.sup.5 .ANG., 1.times.10.sup.5 .ANG., 3.times.10.sup.4 .ANG. 
and 2.times.10.sup.3 .ANG.). 
The calibration of bisphenol-A polycarbonate was used for the 
determination. No large deviations were found compared with the Mw 
determination by the light scattering method.

EXAMPLES 
Example A 1 
Preparation of a dimeric fatty acid polyester containing aliphatic OH end 
groups and having a calculated molecular weight of about 2,000 
20.16 kg (36 mols) of dimeric fatty acid are mixed with 5.664 kg (48 mols) 
of 1,6-hexanediol and the mixture is heated to 150.degree. under nitrogen 
(30 l/hour). Above 150.degree., condensation water starts to distill off 
over a column. The temperature is increased to 200.degree. C. in the 
course of 5 hours and the mixture is left at this temperature for two 
additional hours. After adding 0.258 g of SnCl.sub.2 . 2H.sub.2 O, the 
supply of nitrogen is discontinued and the pressure is reduced gradually 
to 50 mm Hg in the course of 3 hours. After an additional 7 hours at 
200.degree. and under 50 mm Hg, the condensation reaction has ended. 
An oil with a OH number of 57 (calculated: 54.9) and an acid number of 1.9, 
corresponding to an average molecular weight of about 1,900, is obtained. 
The viscosity of this oil as a 50 percent strength solution in xylene is 
19 seconds (measured in a DIN 53 211 flow cup No. 4). 
Example A 2 
Preparation of a dimeric fatty acid polyester containing aliphatic OH end 
groups by azeotropic esterification 
20.16 kg (36 mols) of dimeric fatty acid, 5.664 kg (48 mols) of 
1,6-hexanediol and 4 kg of xylene are mixed and the mixture is slowly 
heated to a reflux temperature of 180.degree., under nitrogen and while 
stirring. Most of the water of condensation can be separated off by a 
water separator in the course of 6 hours. After adding 0.258 g of 
SnCl.sub.2. 2H.sub.2 O, the mixture is heated under reflux for an 
additional 8 hours, until all of the water of condensation has been 
separated off. All the xylene is then distilled off under reduced 
pressure. An oil with an OH number of 57 (calculated: 54.9) and an acid 
number of 1.9, corresponding to an average molecular weight of about 
1,900, is obtained. The viscosity of this oil as a 50 percent strength 
solution in xylene is 19 seconds. 
Example A 3 
Preparation of a dimeric fatty acid polyester containing aliphatic OH end 
groups and having a calculated molecular weight of about 4,000 
4.368 kg (7.8 mols) of dimeric fatty acid, 1.074 kg (9.1 mols) of 
1,6-hexanediol and 0.85 kg of xylene are heated under reflux, while 
stirring, according to Example A 2. After adding 0.056 g of SnCl.sub.2. 
2H.sub.2 O, the process is continued as in Example A 2. The resulting oil 
has an OH number of 30 (calculated: 28.3) and an acid number of 1, 
corresponding to an average molecular weight of 3,600. The viscosity of 
this oil as a 50 percent strength solution in xylene is 29 seconds. 
EXAMPLE A 4 
Esterification of dimeric fatty acid with an excess of 1,6-hexanediol 
5.6 kg (10 mols) of dimeric fatty acid and 3.54 kg (30 mols) of 
1,6-hexanediol are subjected to a condensation reaction according to 
Example A 1, using 0.092 g of SnCl.sub.2 . 2H.sub.2 O as the catalyst. 
The resulting oil has an OH number of 255 (calculated: 255) and an acid 
number of 2. 
The viscosity of this oil as a 50 percent strength solution in xylene is 
15.8 seconds. 
Example A 5 
Preparation of a dimeric fatty acid polyester containing COOH end groups 
and having a calculated molecular weight of about 3,000. 
3.64 kg (6.5 mols) of dimeric fatty acid and 0.614 kg (5.2 mols) of 
hexanediol are subject to a condensation reaction according to Example A 
1, 0.043 g of SnCl.sub.2.2H.sub.2 O being added as the catalyst. 
The resulting oil has an acid number of 37 (calculated: 35.9) and an OH 
number of 1.5, corresponding to an average molecular weight of 2,910. 
The viscosity of this oil as a 50 percent strength solution in xylene is 15 
seconds. 
Example B 1 
Preparation of a polyester of dimeric fatty acid and hexanediol containing 
diphenol carbonate end groups of 2,2-bis-(4-hydropyphenyl)-propane 
(bishpenol-A) and having a calculated molecular weight of about 2,500 
A mixture of 9.9 kg (4.84 mols) of the polyester of dimeric fatty acid and 
hexanediol from Example A 1, 2.074 kg (9.68 mols) of diphenyl carbonate 
and 2.21 kg (9.68 mols) of bisphenol-A is initially introduced into an 
autoclave. The mixture is melted at 100.degree., while compensating the 
pressure with nitrogen. 1.54 ml of 40 percent strength NaOH (35 ppm of Na, 
relative to the weight of materials used) are added to this melt as a 
catalyst. The pressure is now slowly reduced to 1-1.5 mm Hg in the course 
of 1 hour . Thereafter, the reaction mixture is heated to an internal 
temperature of 150.degree. in the course of 1 hour, until the phenol 
formed has distilled off. The reaction mixture is kept at this temperature 
and under 1-1.5 mm Hg for an additional 2 hours, until most of the phenol 
has been split off. Thereafter, a vacuum of 0.5 mm Hg is applied and the 
condensation reaction is continued at 150.degree. for 2 hours. When the 
reaction has ended, 1.793 g of phenol (98.4% of theoretical) have been 
distilled off. 
The oil isolated has an OH number of 46 (calculated: 44) and an acid number 
of 1, corresponding to an average molecular weight Mn of 2,383. 
The viscosity of the isolated oil as a 50 percent strength solution in 
xylene is 70 seconds (measured in a DIN 53 211 flow cup No. 4). 
Example B 2 
Preparation of a polyester of dimeric fatty acid and hexanediol containing 
diphenol carbonate end groups of bishpenol-A and having a calculated 
molecular weight of about 2,500 
9.9 kg (4.84 mols) of the polyester of dimeric fatty acid and hexanediol 
from Example A 2 (prepared by azeotropic esterification), 2.074 kg (9.68 
mols) of diphenyl carbonate, 2.21 kg (9.68 mols) of bisphenol-A and 1.54 
ml of 40 percent strength NaOH are reacted analogously to Example B 1. 
After distilling off 1.800 kg (98.8% of theoretical) of phenol, an oil with 
an OH number of 46 (calculated: 44) and an acid number of 1, corresponding 
to an average molecular weight Mn of 2,383, is obtained. 
The viscosity of this oil as a 50 percent strength solution in xylene is 70 
seconds. 
Example B 3 
Preparation of a polyester of dimeric fatty acid and hexanediol containing 
diphenol carbonate end groups of 2,2-bis-(4-hydroxyphenyl)-propane 
(bisphenol-A) and having a calculated molecular weight of about 4,400 
4.61 kg (1.16 mols) of dimeric fatty acid polyester from Example A 3, 0.497 
kg (2.32 mols) of diphenyl carbonate, 0.530 kg (2.32 mols) of bisphenol-A 
and 0.6 ml of 40 percent strength NaOH (35 ppm of Na, relative to the 
weight of materials used) are reacted analogously to Example B 1. After 
distilling off 421 g of phenol (96.3% of theoretical), an oil with an OH 
number of 27 (calculated: 25) and an acid number of 1, corresponding to an 
average molecular weight Mn of 4,000, is obtained. 
The viscosity of this oil as a 50 percent strength solution in xylene is 
182 seconds. 
Example B 4 
Preparation of an aliphatic polyester-polycarbonate of dimeric fatty acid 
and hexanediol containing diphenol carbonate end groups and having a 
calculated molecular weight of about 3,200 
6.24 kg of the mixture of 1,6-hexanediol and the ester of dimeric fatty 
acid and hexanediol from Example A 4, 3,551 kg (16.6 mols) of diphenyl 
carbonate, 1.082 kg (4.74 mols) of bisphenol-A and 1.7 ml of 40 percent 
strength NaOH (50 ppm of Na, relative to the weight of materials used) are 
reacted analogously to Example B 1. After splitting off 3.115 kg of phenol 
(99.8% of theoretical), an oil with an OH number of 35 (calculated: 34.3), 
corresponding to an average molecular weight Mn of 3,200, is obtained. 
The viscosity of this oil as a 50 percent strength solution in xylene is 
114 seconds. 
Example C 1 
Preparation of a high-molecular, segmented polycarbonate elastomer 
consisting of 55% by weight of a polyester of dimeric fatty acid and 
hexanediol (molecular weight: about 2,000) and 45% by weight of 
bisphenol-A polycarbonate 
3.094 kg of the precursor from Example B 1 are dissolved in 30 l of 
methylene chloride and the solution is added to a solution of 1.265 kg 
(5.54 mols) of bisphenol-A, 29.89 g of p-tert.-butylphenol, 1.415 kg of 45 
percent strength NaOH and 30 1 of distilled water. 1.181 kg (11.95 mols) 
of phosgene are passed in at 20.degree.-25.degree. in the course of 25 
minutes, while stirring and under a nitrogen atmosphere. During the 
introduction, 2.22 kg of 45 percent strength NaOH are simultaneously added 
dropwise such that the pH value remains constant at 13. After passing in 
the phosgene, 8.05 g of triethylamine are added and the mixture is stirred 
for 1 hour. 
The organic phase is separated off and washed first with 2 percent strength 
phosphoric acid and then with distilled water, until free from 
electrolytes. After separating off the water, the organic solution is 
concentrated. The high-molecular, segmented polycarbonate elastomer is 
isolated by extrusion in an evaporation extruder at about 
230.degree.-250.degree. under the conditions known for polycarbonate 
extrusion. 
The analytical data for the polycarbonate elastomer are: relative viscosity 
(0.5% strength in CH.sub.2 Cl.sub.2): .eta..sub.rel =1.53; Mn: 15,637; Mw: 
123,626; H (heterogeneity):6.91. 
Differential thermoanalysis (DTA) of this product shows that phase 
separation of the soft segment consisting of the polyester of dimeric 
fatty acid and hexanediol (glass transition temperature: -50.degree.) from 
the bisphenol-A polycarbonate hard segment (glass transition temperature: 
about 135.degree.-140.degree.) is present both during the first heating 
and during the second heating. 
The material obtained is in the form of odorless, free-flowing granules 
suitable for further processing, for example, into extruded films. 
Production and testing of fine films of the polycarbonate elastomers 
according to the invention: 
The resulting granules were extruded at between 200.degree.and 250.degree. 
C. to yield flat films 200 .mu.m thick. 
Optical measurements on the extruded films gave light transmissions of up 
to 90% and turbidities of only 2%. 
Tensile strength: 20 MPa, measured in accordance with the method of DIN 53 
504 
Elongation at break: 700%, measured in accordance with the method of DIN 53 
504 
Tear propagation resistance according to Graves: 25 kN/m 
Flexible bags were produced from the films by means of heat impulse welding 
and were filled with 1 liter of water and subjected to steam sterilization 
in accordance with the method of DIN 58 946, Part 1,Ile. The bags passed 
subsequent drop tests in accordance with the method of DIN E 58 361, Part 
4.The films produced with the material according to the invention meet the 
chemical requirements of transfusion containers in accordance with DIN E 
58 361, Part 4. 
Permeability to steam, based on a thickness of 100 .mu.m: 18 
g.m.sup.-2.d.sup.-1. 
The present bags exhibit an exceptionally good low temperature flexibility. 
Example C 2 
Preparation of a high-molecular, segmented polycarbonate elastomer 
consisting of 55% by weight of a polyester of dimeric fatty acid and 
hexanediol (molecular weight: about 2,000/prepared by azeotropic 
esterification) and 45% by weight of bisphenol-A polycarbonate 
A high-molecular polycarbonate elastomer was prepared from 3.094 kg of the 
precursor from Example B 2, 1.265 kg of bisphenol A, 29-89 g of 
p-tert.-butylphenol and 1.181 kg of phosgene analogously to Example C 1. 
The properties of the product otherwise correspond to those of the product 
from Example C 1. The relative viscosity .eta..sub.rel of this product is 
1.53. 
Example C 3 
Preparation of a high-molecular polycarbonate elastomer consisting of 55% 
by weight of a polyester of dimeric fatty acid and hexanediol (molecular 
weight: about 4,000) and 45% by weight of bisphenol-A polycarbonate 
2.794 kg of the precursor from Example B 3 are dissolved in 30 liters of 
methylene chloride and the solution is added to a solution of 1.532 kg 
(6.7 mols) of bisphenol-A, 41.85 g of p-tert.-butylphenol and 1.415 kg of 
45 percent strength NaOH and 30 liters of distilled water. 1.181 kg of 
phosgene are passed in at 20.degree.-25.degree. in the course of 25 
minutes, while stirring and under a nitrogen atmosphere. During this 
introduction, the pH value is kept constant at 13 with 2.22 kg of 45 
percent strength NaOH. After adding 8.05 g of triethylamine, the mixture 
is worked up as in Example C 1. 
The analytical data of the polycarbonate elastomer are: relative viscosity 
(0.5% strength in CH.sub.2 Cl.sub.2): .eta..sub.rel =1.49; Mn: 10,878; Mw: 
115,034; H (heterogeneity): 9.57. 
Differential thermoanalysis of this product shows that a phase separation 
of the soft segment consisting of the polyester of dimeric fatty acid and 
hexanediol (glass transition temperature: -50.degree.) from the hard 
segment (glass transition temperature: about 135.degree.-140.degree.) is 
present both during the first heating and during the second heating. 
Example C 4 
Preparation of a high-molecular, segmented polycarbonate elastomer 
consisting of 55% by weight of an aliphatic dimeric fatty acid 
ester-polycarbonate (molecular weight: 2,600) as the soft segment and 45% 
by weight of bisphenol-A polycarbonate 
3.089 kg of the precursor from Example B 4 are dissolved in 30 liters of 
methylene chloride and the solution is added to a solution of 1.406 kg of 
bisphenol-A, 29.9 g of p-tert.-butylphenol and 1.415 kg of 45 percent 
strength NaOH, and 30 liters of distilled water. The reaction is continued 
using the same amounts of phosgene, sodium hydroxide solution and 
triethylamine as in Example C 1 and under the reaction conditions of 
Example C 1. 
The relative viscosity .eta..sub.rel of the polycarbonate elastomer 
containing dimeric fatty acid units is 1.70. Differential thermoanalysis 
shows that a phase separation of the soft segments (glass transition 
temperature: -40.degree.) from the hard segment (glass transition 
temperature: about 130.degree.-140.degree.) is present both during the 
first heating and during the second heating. 
Example C 5 
Preparation of a polycarbonate elastomer from a dimeric fatty acid 
polyester containing carboxyl end groups (molecular weight: about 3,100), 
bisphenol-A and phosgene 
A solution of 13.75 g of the polyester, from Example A 5 of dimeric fatty 
acid and hexanediol containing carboxyl end groups and 225 g of methylene 
chloride is added to a solution of 10.09 g of bisphenol-A, 44.2 ml of 2N 
NaOH and 130 ml of distilled water. 10.45 g of phosgene are passed in at 
20.degree.-25.degree. in the course of 20 minutes, while stirring and 
under a nitrogen atmosphere, and at the same time 37 g of 45 percent 
strength NaOH are added dropwise in order to maintain a constant pH of 13. 
After passing in the phosgene, 7.3 ml of a 1 percent strength 
triethylamine solution are added and the mixture is stirred for 1 hour. 
The organic phase is separated off and washed successively with distilled 
water until free from electrolytes. After concentrating, the residue is 
dried in a vacuum drying cabinet at 50.degree. and under 15 mm Hg for 12 
hours. 
The relative viscosity .eta..sub.rel of the product is 1.61. 
Example C 6 
Preparation of a polycarbonate elastomer from the bischlorocarbonic acid 
ester of a dimeric fatty acid polyester, bisphenol-A and phosgene by the 
phase boundary process 
4 g of phosgene are passed into a solution of 13.75 g of the polyester of 
dimeric fatty acid and hexanediol of Example A 1 and 225 g of methylene 
chloride. After stirring the mixture for 5 minutes, a solution of 10.09 g 
of bisphenol-A, 44.2 ml of 2N NaOH, 130 ml of distilled water and, as a 
catalyst, a mixture of 0.08 g of tributylamine and 0.14 g of 
tetrabutylammonium bromide is added. After stirring the reaction mixture 
for a further period of 5 minutes, 6.59 g of phosgene are passed in over a 
period of 15 minutes, and at the same time 27 g of 45 percent strength 
NaOH are added dropwise in order to maintain a constant pH of 13. After 
passing in the phosgene, the mixture is stirred for an additional hour and 
worked up as described in Example C 5. 
The relative viscosity .eta..sub.rel of the product is 1.31. 
4.5 ml of a 1 percent strength triethylamine solution can also be equally 
successfully employed as a catalyst in the reaction, analogously to the 
catalyst combination of tetrabutylammonium bromide and triethylamine. 
The relative viscosity .eta..sub.rel of the product is 1.32. 
Example C 7 
Preparation of a polycarbonate elastomer from a dimeric fatty acid 
polyester containing aliphatic hydroxyl end groups, bisphenol-A and 
phosgene by the pyridine process 
10.09 g of bisphenol-A are dissolved in 170 g of pyridine, under a nitrogen 
atmosphere. A solution of 13.75 g of the polyester of dimeric fatty acid 
and hexanediol of Example A 2 and 225 g of methylene chloride is added to 
that solution. 5.1 g of phosgene are then passed into this reaction 
solution in the course of 20 minutes while stirring. The reaction mixture 
formed is stirred for a further period of one hour. The pyridine 
hydrochloride formed during the reaction is then filtered off and the 
organic phase is washed twice with 10 percent strength hydrochloric acid. 
Thereafter, the organic phase is washed with distilled water until free 
from electrolytes. The product is isolated according to Example C 5 
The relative viscosity .eta..sub.rel of the polycarbonate elastomer is 
1.33. 
Example C 8 
Preparation of a segmented, aromatic polycarbonate consisting of 20% by 
weight of a polyester of dimeric fatty acid and hexanediol (molecular 
weight: about 2,000) and 80% by weight of bisphenol-A polycarbonate 
6.25 g of the precursor from Example B 1 are dissolved in 225 g of 
methylene chloride and that solution is added to a solution of 16.83 g of 
bisphenol-A, 0.378 g of p-tert.-butylphenol, 78.5 ml of 2N NaOH and 90 g 
of distilled water. 11.7 g of phosgene are passed in at 
20.degree.-25.degree. in the course of 20 minutes, while stirring and 
under a nitrogen atmosphere. During this introduction, the pH value is 
kept constant at 13 by the addition of 16 g of 45 percent strength NaOH. 
After adding 8 g of a 1% strength triethylamine solution, the mixture is 
stirred for an additional hour. The product is isolated according to 
Example C 5. 
The relative viscosity .eta..sub.rel of the segmented, aromatic 
polycarbonate is 1.34. 
Differential thermoanalysis shows that a phase separation of the soft 
segment (glass transition temperature: -52.degree. C.) from the aromatic 
polycarbonate hard segment (glass transition temperature 135.degree. C.) 
is present both during the first heating and during the second heating. 
Example C 9 
Preparation of an aromatic polycarbonate consisting of 3% by weight of a 
polyester of dimeric fatty acid and hexanediol (molecular weight: about 
2,000) and 97% by weight of bisphenol-A polycarbonate 
0.94 g of the precursor from Example B 1 is dissolved in 225 g of methylene 
chloride and then added to a solution of 21.6 g of bisphenol-A, 0.458 g of 
p-tert.-butylphenol, 95 ml of 2N NaOH and 75 g of distilled water. 14.15 g 
of phosgene are passed in at 20.degree.-25.degree. C. in the course of 20 
minutes, while stirring and under a nitrogen atmosphere. During this 
introduction, the pH value is kept constant at 13 by the addition of 22 g 
of 45% strength NaOH. After adding 9.5 g of a 1% strength triethylamine 
solution, the mixture is stirred for a further period of one hour. The 
product is isolated according to Example C 5. 
The relative viscosity .eta..sub.rel of the aromatic polycarbonate is 1.30.