Novel polyesteramides having low glass transition temperatures

Random or regularly recurring block polyesteramides having glass transition temperatures at least as low as -30.degree. C. are prepared from (i) essentially difunctional monomers comprising at least one carboxylic acid function, or ester/amide-forming derivative thereof, at least 1 mol % of which comprising dicarboxylic acids or such derivatives thereof and having from 20 to 60 carbon atoms, with the amount of monofunctional carboxylic acids comprising said carboxyl monomers being less than about 1% by weight and the amount of carboxylic acids having in excess of two functional groups being less than about 5% by weight, and (ii) a member selected from the group consisting of dihydroxyl and diamino comonomers therefor, or aminoalcohol comonomers, or mixtures of diamino and aminoalcohol comonomers.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
The present invention relates to novel copolyesteramides having a random or 
alternately regularly recurring block structure, and which have a high 
molecular weight and significant flexibility and elasticity down to 
temperatures which are below or equal to -30.degree. C. 
2. Description of the Prior Art 
Copolyesteramides having glass transition temperatures below 0.degree. C. 
have already been described in the literature. For example, U.S. Pat. No. 
3,650,999 notes block copolyesteramides, the crystalline phase of which 
consists of polyester units and the amorphous phase consisting of 
polyamide units. However, copolymers of this type lose all flexibility and 
pliability at between -10.degree. C. and -20.degree. C. Furthermore, their 
relatively low molecular weight only enables them to be used as adhesives. 
Likewise, French Pat. No. 77/22,305 describes thermoplastic elastomers 
consisting of block copolyesteramides. These polymers possess valuable 
properties, in particular flexibility at low temperature. However, their 
moduli are not generally sufficiently low and their heterogeneity in 
molten state makes them difficult to prepare. 
Thus, for certain applications, serious need exists in this art for 
thermoplastic elastomers which have good cohesion while at the same time 
remain pliable down to temperatures below -30.degree. C. 
SUMMARY OF THE INVENTION 
Accordingly, a major object of the present invention is the provision of 
novel polyesteramides having a random or alternately regularly recurring 
block structure, and having a glass transition temperature below 
-30.degree. C., such polyesteramides being characterized in that they are 
prepared from (i) essentially difunctional reactants or monomers which 
have at least one carboxylic acid group, or ester- or amide-forming 
derivative thereof, at least 1 mol % of which comprising diacids, or such 
derivatives thereof, having from 20 to 60 carbon atoms, with the amount of 
monofunctional carboxylic acids comprising said carboxyl reactants being 
less than about 1% by weight, preferably less than about 0.2% by weight, 
and the amount of carboxylic acids having in excess of two functional 
groups being less than about 5% by weight, preferably less than about 3% 
by weight, and (ii) either dihydroxyl and diamino comonomers, or 
aminoalcohol comonomers, or mixtures of diamino and aminoalcohol 
comonmers. 
DETAILED DESCRIPTION OF THE INVENTION 
More particularly according to this invention, by the expression 
"essentially difunctional monomers" there is intended that, among such 
reactants comprising an acid function, there can be included a minor 
proportion of monofunctional or polyfunctional reactants or monomers, 
provided that the characteristics of the resultant polyesteramide obtained 
with these mixtures are essentially unmodified vis-a-vis a polyesteramide 
prepared from only difunctional reactants. 
By the expression "comprising at least one carboxylic acid function" there 
is intended that the essentially difunctional monomers can contain, in 
addition to a carboxyl group, ester-forming or amide-forming groups, 
hydroxyl or amine groups, or derivatives thereof. 
The expression "acid group or derivative thereof" is intended to connote 
anhydride, ester or lactam groups. 
Dimeric acids are preferred among the diacids having from 20 to 60 carbon 
atoms. 
The term "dimeric acids" is intended to connote polymeric fatty acids 
obtained by the fractionation of fatty acids and containing more than 
about 95% by weight of dimers. The term fatty acids is intended to connote 
saturated or unsaturated aliphatic monoacids having from 8 to 24 carbon 
atoms. 
Among the linear or branched chain saturated fatty acids envisaged, 
representative are: caprylic, pelargonic, capric, lauric, myristic, 
palmitic and isopalmitic, stearic, arachidic, behenic and lignoceric 
acids. 
Among the linear or branched chain fatty acids having ethylenic 
unsaturation, representative are: oct-3-enoic, dodec-11-enoic, lauroleic, 
myristoleic, palmitoleic, gadoleic, cetoleic, linoleic, linolenic, 
eicosatetraenoic and chaulmoogric acids. Certain acids having acetylenic 
unsaturation can also provide polymeric acids, but these do not exist as a 
practical matter in the natural state and their economic value is 
therefore very low. 
The polymeric fatty acids obtained by polymerization, most typically in the 
presence of peroxides or Lewis acids, can be fractionated. They can also 
be hydrogenated in order to reduce their degree of unsaturation and thus 
to reduce their coloration. 
The most advantageously used starting materials are hydrogenated 
compositions derived from oleic and linoleic acids and which contain: from 
1 to 15% by weight of monobasic acid, from 80 to 98% by weight of dibasic 
acid and from 1 to 25% by weight of tribasic acid or acids of higher 
basicity. 
Compositions in which the fraction of dimeric acid is greater than 95% will 
preferably be used according to the invention. Dimeric acids in which the 
proportion of monofunctional acid is less than 1% by weight, and in which 
the proportion of acid with more than two functional groups is less than 
5% by weight and preferably less than 3% by weight, are more preferred. 
The other reactants containing carboxylic acid groups can be diacids, 
aminoacids, aminoalcohols or their ester-forming or amide-forming 
derivatives. These reactants can have an aliphatic or cycloaliphatic chain 
or a chain of aromatic structure, which is not directly bonded to the 
functional groups. 
The dihydroxyl compounds are essentially compounds with an aliphatic, 
cycloaliphatic or aromatic chain which is not directly bonded to the 
hydroxyl groups, and having a molecular weight which is typically less 
than 500, or macromolecular dihydroxyl compounds having a molecular weight 
which is generally between 500 and 5,000, such as, for example, 
polyether-diols, such as tetrahydrofuran, polyoxyethylene glycols, 
polyoxypropylene glycols or polylactones. 
The diamine compounds are selected from among diamines with an aliphatic or 
cycloaliphatic chain or a chain of aromatic structure, which is not 
directly bonded to the amino groups. 
Likewise, the aminoalcohols have an aliphatic or cycloaliphatic chain or a 
chain of aromatic structure, the amine group not being bonded directly to 
the ring. 
The copolymers according to the invention can possess both good cohesion 
and good pliability. To do this, a compromise must be found in the 
relative proportions of the polyester segments and the polyamide segments. 
The proportion by weight of polyester segments will advantageously be 
between 20% and 80% and, if it is desired to prepare elastomers of low 
moduli, preferably between 50% and 80%. 
For the calculation of these proportions by weight of ester and amide 
segments, it will be assumed that the ester segments are derived from a 
carboxylic acid by the loss of one OH and from an alcohol by the loss of 
one H, that the amide segments are derived from a carboxylic acid by the 
loss of one OH and from an amine by the loss of one H, and that the 
structures forming part of both ester and amide segments, with the 
exception of the --CO--, --NH-- and --O-- groups (functional radicals), 
are divided up equally between these ester and amide segments. 
In the polyesteramides according to the invention, the cohesion is 
essentially provided by the amide segments. Thus, in the proportions by 
weight indicated above, which are between 20 and 80%, it will also be 
possible to vary the composition of the amide segments, within certain 
limits, in order to obtain the selected mechanical properties. It will 
thus also be possible to increase the cohesion by selecting, for the 
production of amide segments, a proportion, which can range up to 99% of 
the reactants with carboxylic acid groups or derivatives thereof, of 
diacids or aminoacids or lactams with short claims which can have, for 
example, a number of carbon atoms which is less than or equal to 12. 
Short-chain acids which are representative are oxalic, malonic, succinic, 
glutaric, adipic, pimelic, suberic, azelaic, sebacic and dodecanedioic 
acids, and aminoacids which are representative are aminocaproic acid, 
9-aminononanoic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid. 
Lactams which are representative are caprolactam, enantholactam, 
capryllactam, .omega.-aminopelargonic acid, .omega.-aminoundecanoic acid 
or lauryllactam. 
Various processes can be used for the preparation of the polyesteramides 
according to the invention. 
The presence of dimeric acid generally increases the compatibility of the 
various constituents and makes it possible to obtain polymers of high 
molecular weight with reaction times, in vacuo, which are generally less 
than 2 or 3 hours. The secondary reactions leading to highly colored 
products of low molecular weight, which reactions are frequent during the 
preparation of polyesteramides obtained from diacids having fewer than 6 
carbon atoms and of diols with short chains (of less than or equal to 4 
carbons), are of little importance, if not nonexistent, in the case of the 
polyesteramides according to the invention. The structures obtained 
furthermore have a good stability to hydrolysis. 
The polycondensation/esterification reaction can be carried out from a 
mixture of all of the reactants, in which case an essentially random 
structure is obtained. 
It is also possible to initially form amide blocks and then to carry out 
the esterification reaction, in which case an essentially random block 
structure is obtained if the amide blocks have acid end groups, or an 
essentially alternately block structure is obtained if the amide blocks 
are first esterified. A process of this type is described in U.S. Pat. No. 
3,849,514. 
It is also possible to start from preformed diesteramides, such as those 
described in Belgian Pat. No. 857,005, the general formula of which is: 
EQU CH.sub.3 --O--CO--R--CO--NH--(CH.sub.2).sub.n --NH--CO--R--CO--O--CH.sub.3 
in which n is an integer between 2 and 12 inclusive and R is a divalent 
aliphatic radical (CH.sub.2).sub.m, m being an integer between 2 and 12 
inclusive, or a divalent aromatic radical bonded in the meta or para 
positions, or a divalent cycloaliphatic radical bonded in the 1,3-or 
1,4-positions. 
An example of a diesterdiamide of this type is 
N,N'-bis-(para-carbomethoxybenzoyl)-hexamethylenediamine. 
It is also envisaged to couple polyamide blocks and polyester blocks having 
a molecular weight of between 500 and 5,000. 
The diacid having between 20 and 60 carbon atoms can be totally employed in 
the ester sequences or totally employed in the amide sequences or 
distributed between the two types of sequence. 
Depending on the composition and the process used, polyesteramides having 
elastomeric properties which can vary and can be adjusted as desired will 
be obtained. However, the main value of these thermoplastic elastomers is 
that these elastomeric properties are retained down to temperatures of the 
order of -30.degree. C. 
Thus, the polyesteramides with alternate blocks, containing crystalline 
amide blocks obtained from acid reactants having fewer than 12 carbon 
atoms, constitute a particularly valuable class because they also possess 
a very good cohesion. 
The polyesteramides according to the invention can be used in various 
applications in which their good mechanical and impact strength properties 
at low temperature are of value. Used by themselves, these polyesteramides 
make it possible to obtain textile filaments, films, other shaped 
articles, coatings, adhesives and the like. 
With semi-crystalline polyesteramides, it is possible to prepare adhesives 
of the hot melt type or coatings. These polyesteramides can also be used 
to reinforce numerous other polymers, such as polyamides or polyolefins, 
imparting a combination of particularly valuable properties to the 
compositions thus obtained. 
In order to further illustrate the present invention and the advantages 
thereof, the following specific examples are given, it being understood 
that same are intended only as illustrative and in nowise limitative.

In the following examples, a certain number of determinations were carried 
out. Likewise, various properties were measured. The procedures or 
specifications in accordance with which the aforesaid determinations and 
measurements were carried out are indicated below. 
1. Determination of inherent viscosity 
The dried polymer is dissolved in meta-cresol in such amount as to provide 
a 0.5% strength solution. The flow time of this solution is measured in 
comparision with that of the pure solvent. The value of the inherent 
viscosity is given by the formula: 
EQU .eta.inh.=4.6 (log t.sub.1 -log t.sub.0) 
EQU t.sub.1 =flow time of the solution 
EQU t.sub.0 =flow time of the solvent 
It is expressed in dl/g. 
2. Microcalorimetric analysis 
The polymers or the mixtures of polymers are characterized by their 
intrinsic viscosity and also by melting characteristics, such as the 
melting endotherms Em. 
These determinations are carried out on a sample subjected to both 
increasing and decreasing temperature variations of 10.degree. C./minute. 
A curve, on which the melting endotherms can be identified, is thus 
determined by differential microcalorimetry. 
3. Glass transition temperature 
The glass transition temperature corresponds to the sudden drop in the 
shear modulus as a function of the temperature. It can be determined from 
the graph representing the variations in the torsional modulus as a 
function of the temperature, these variations being measured by 
thermomechanical analysis using an automatic torsion pendulum. 
4. Softening point 
This is determined using a Kofler bench. 
5. Shear modulus under torsion 
This is determined at three temperatures, namely, at -20.degree. C., 
0.degree. C. and +20.degree. C., using an automatic torsion pendulum at a 
frequency of the order of 1 Hertz, in accordance with ISO Standard 
Specification R 537. 
6. Determination of end groups 
NH.sub.2 : Automatic potentiometric determination of the solution of 
polymer in a 90/10 by weight mixture of phenol and water, using HCl. The 
result is given in milligram equivalents per 10.sup.3 g of polymer. 
COOH: Hot dissolution of the polymer in benzyl alcohol, under a nitrogen 
atmosphere, and acidimetric determination of this hot solution, under 
nitrogen, using a glycolic solution of potassium hydroxide in the presence 
of phenolphthalein. The result is given in miligram equivalents per 
10.sup.3 g of polymer. 
EXAMPLE 1 
Preparation of polyesteramide from dimeric acid, hexane-1,6-diol and 
hexamethylenediamine 
The reaction was carried out in a stirred glass reactor adopted for 
operation in vacuo. 
The following ingredients were introduced at ambient temperature: 
(i) 40.3 g (0.07 mol) of a fatty acid dimer having a monomer content of 
0.03% and a trimer content of about 3% (marketed by Unilever Emery under 
the name Empol 1010); this acid dimer, which will be referred to as 
"dimeric acid", was used in the following examples; 
(ii) 4.06 g (0.035 mol) of hexamethylenediamine; 
(iii) 5.9 g (0.05 mol) of hexane-1,6-diol; and 
(iv) 10 mg of titanium glycolate (catalyst). 
The apparatus was carefully purged with nitrogen, the reaction mass was 
stirred and its temperature was raised to 260.degree. C. over the course 
of 1 hour 30 minutes. A vacuum was then established until it reached 0.5 
mm of mercury, and polycondensation was carried out at 260.degree. C. for 
1 hour 30 minutes. The resulting polymer was homogenous and possessed 
rubbery properties. Its characteristics are reported in the Table which 
follows. 
EXAMPLE 2 
Preparation of polyesteramide from dimeric acid, ethylene glycol and 
hexamethylenediamine 
The reaction was carried out in a 7.5 liter stainless steel autoclave 
fitted with an anchor-type stirrer equipped with a tachometric dynamo. 
The following reactants were introduced into the autoclave at ambient 
temperature: 
______________________________________ 
Dimeric acid: 892.04 g (1.289 mols) 
Pure crystalline hexa- 
methylenediamine: 141.23 g (1.217 mols) 
______________________________________ 
The amount of these reactants introduced was calculated such as to provide 
a prepolyamide having a molecular weight of 3,000, and containing COOH end 
groups. 
The reactants were introduced at ambient temperature, the apparatus was 
carefully purged with nitrogen and the temperature of the reaction mass 
was then raised to 270.degree. C. over the course of 2 hours, under 
stirring. The reaction mass was subsequently maintained at 270.degree. for 
45 minutes and then reduced to ambient temperature. 
The following reactants were then introduced into the autoclave: 
______________________________________ 
Dimeric acid: 1,915.6 g 
(3.323 mols) 
Ethylene glycol: 339.7 g (5.478 mols) 
Titanium glycolate: 
0.5 g 
______________________________________ 
The apparatus was again carefully purged with nitrogen and the temperature 
of the reaction mass was then raised to 200.degree. C. over the course of 
1 hour 15 minutes, under stirring, in order to effect distillation of the 
water of reaction. The temperature was then raised to 270.degree. over the 
course of 1 hour 15 minutes. A vacuum was then established over the course 
of 1 hour 30 minutes until it reached 0.4-0.5 mm Hg. Polycondensation was 
then carried out at 270.degree. C. for 1 hour 15 minutes under 0.4-0.5 mm 
Hg. 
The polymer was subsequently drawn off under nitrogen pressure and 
collected in water, and it was then converted to granules after cooling in 
liquid nitrogen. 
The characteristics of the resulting product are reported in the Table 
which follows. 
EXAMPLE 3 
Preparation of polyesteramide from dimeric acid, sebacic acid, ethylene 
glycol and hexamethylenediamine (HMD) 
In a first stage, a polyamide of dimeric acid/sebacic acid (70/30 w/w) and 
hexamethylenediamine was prepared under the conditions required to obtain 
a molecular weight of 2,000 and a polyamide with COOH end groups. 
The following reactants were introduced into a 1 liter Pyrex reactor at 
ambient temperature: 
______________________________________ 
Dimeric acid: 319.4 g (0.554 mol) 
Sebacic acid: 260.2 g (1.288 mols) 
Pure crystalline HMD: 
170 g (1.467 mols) 
______________________________________ 
The apparatus was carefully purged with nitrogen and the temperature of the 
mass was raised to 265.degree. over the course of 2 hours, under stirring. 
The resulting reaction mass was perfectly homogeneous. Same was maintained 
at 265.degree. C. for 1 hour 15 minutes. The resulting polymer was drawn 
off into water and then ground and dried at 100.degree. in an oven in 
vacuo. The characteristics of the resulting copolyamide were as follows: 
______________________________________ 
COOH end groups: 982.5 meq/kg 
NH.sub.2 end groups: 2.8 meq/kg 
Mp by differential thermal 
analysis: 185.degree. C. 
Molecular weight based 
on end groups: 2,070 
______________________________________ 
The following reactants were introduced into a 7.5 liter stainless steel 
autoclave at ambient temperature: 
______________________________________ 
Prepolyamide, previously 
prepared: 522.6 g 
Ethylene glycol: 307.7 g (4.962 mols) 
Dimeric acid: 1,744.5 g 
(3.026 mols) 
Titanium glycolate: 
0.414 g 
______________________________________ 
The apparatus was carefully purged with nitrogen, the reaction mass was 
stirred and the temperature of the reaction mass was raised to 270.degree. 
C. over the course of 2 hours 15 minutes. A vacuum was established over 
the course of 1 hour 15 minutes until it reached 0.3 mm Hg. Stirring was 
maintained for 2 hours 30 minutes at 270.degree. C. under 0.3 mm Hg. The 
polymer was subsequently drawn off under nitrogen pressure, collected in 
water and then converted to granules after cooling with liquid nitrogen. 
The characteristics of the resulting product are also reported in the Table 
which follows. 
EXAMPLE 4 
Preparation of polyetheresteramide from dimeric acid, polytetrahydrofuran 
(poly-THF), sebacic acid and ethylene glycol 
(1) Condensation of dimeric acid and poly-THF of molecular weight 2,000: 
The following reactants were introduced into a 7.5 liter stainless steel 
autoclave: 
______________________________________ 
Dimeric acid: 1,180.7 g 
(2.048 mols) 
Poly-THF (of trade- 
mark TERACOL 2000): 
2,048 g (1.024 mols) 
______________________________________ 
The apparatus was carefully purged with nitrogen, the reaction mass was 
stirred and its temperature was raised to 250.degree. C. over the course 
of 2 hours. A vacuum was then established over the course of 1 hour until 
it reached 0.3 mm Hg. The reaction mass was maintained at 250.degree. C. 
for 2 hours under 0.3 mm Hg. The reaction mass was then reduced in 
temperature back to ambient temperature. The determination of the COOH 
groups, carried out on the residue, indicated 0.0642 COOH/100 g. 
(2) 2,800 g of the product prepared above were retained in the same 
autoclave and the following reactants were then added thereto: 
______________________________________ 
Polyamide of dimeric acid/ 
sebacic acid and hexa- 
methylenediamine, of 
molecular weight 2,000 and 
containing COOH end groups 
(identical to the poly- 
amide described in the 
preceding example): 650 g (0.06857 COOH) 
Ethylene glycol: 154 g (2.4833 mols) 
Titanium glycolate: 0.945 g 
______________________________________ 
The apparatus was carefully purged with nitrogen and the temperature of the 
reaction mass was raised to 250.degree. C. over the course of 1 hour and 
then maintained for 1 hour. A vacuum was then established over the course 
of 1 hour 15 minutes until it reached 0.3 mm Hg. Polycondensation was 
carried out at 250.degree. C. for 1 hour 45 minutes under 0.3 mm Hg. The 
polymer was drawn off under nitrogen pressure, cooled in water and then 
converted to granules after being conveyed through a mixture of acetone 
and solid carbon dioxide. The characteristics of the resulting product are 
also reported in the Table which follows. 
EXAMPLE 5 
Preparation of polyetheresteramide from poly-THF, sebacic acid and ethylene 
glycol 
(a) Condensation of dimeric acid and poly-THF (of molecular weight 1,000): 
The following reactants were introduced into a 7.5 liter autoclave: 
______________________________________ 
Dimeric acid: 1,634 g (2.384 mols) 
Poly-THF (TERACOL 1000): 
1,417 g (1.417 mols) 
______________________________________ 
The procedure was identical to that described above. The determination of 
the COOH groups, carried out on the residue, indicated a proportion of 
0.0877 COOH per 100 g. 
(b) 2,796 g of the above product were retained in the same autoclave and 
the following reactants were added: 
______________________________________ 
Polyamide of dimeric acid/ 
sebacic acid and hexa- 
methylenediamine, of 
molecular weight 2,000 and 
containing COOH end groups: 
649 g 
Ethylene glycol: 194 g 
Titanium glycolate: 0.945 g 
______________________________________ 
The procedure was identical to that described above. Polycondensation was 
carried out at 250.degree. C. for 2 hours 40 minutes under 0.1-0.15 mm Hg. 
The product was collected under the same conditions and the 
characteristics thereof are also reported in the Table which follows. 
EXAMPLES 6 AND 7 
Polyesteramide from N,N'-bis-(carbomethoxybenzoyl)hexamethylenediamine, 
hexane-1,6-diol and dimeric acid 
This type of polyesteramide consisted of rigid units obtained by reacting: 
##STR1## 
and of flexible units obtained by reacting dimeric acid and 
hexane-1,6-diol. 
It should be noted that it is possible, depending on the composition, to 
obtain a whole range of products, the rigidity of which decreases when the 
proportion of flexible units increases. 
EXAMPLE 6 (75% of flexible units/25% of rigid units) 
The following ingredients were introduced, at ambient temperatures, into a 
stirred 100 ml Pyrex reactor equipped for operation under high vacuum: 
______________________________________ 
N,N'-Bis-(carbomethoxy- 
benzoyl)-HMD: 8.91 g 
Hexane-1,6-diol: 11.64 g 
Titanium glycolate: 10 mg 
______________________________________ 
After nitrogen purge, the temperature was raised to 240.degree. over the 
course of 1 hour 15 minutes, under stirring, and stirring was contained at 
240.degree. C. for 1 hour. The resulting reaction mass was perfectly 
limpid. 
The reaction mass was decreased in temperature back to ambient temperature 
and 26.2 g (0.0455 mol) of dimeric acid were added. The apparatus was 
again purged with nitrogen and the temperature was raised to 270.degree. 
over the course of 1 hour 30 minutes, under stirring, and maintained at 
270.degree. for 1 hour. A vacuum was established over the course of 30 
minutes until it reached 0.3 mm Hg, and polycondensation was carried out 
at 270.degree. C. for 2 hours under 0.25-0.3 mm Hg. The reaction mass 
obtained upon completion of the reaction was homogeneous. When cold, the 
product was pliable and retained good properties up to a temperature of 
150.degree.-160.degree. C. 
EXAMPLE 7 (50% of flexible units/50% of rigid units) 
The following ingredients were introduced into a reactor identical to the 
previous reactor: 
______________________________________ 
N,N'-Bis-(carbomethoxy- 
benzoyl)-HMD: 17.81 g (0.0404 mol) 
Hexane-1,6-diol: 12.54 g (0.1062 mol) 
Titanium glycolate: 10 mg 
______________________________________ 
The procedure was identical to that described above. 
For the 2nd stage, dimeric acid (0.03067 mol) was added and 
polycondensation was carried out at 270.degree. C. for 1 hour 30 minutes 
under 0.2-0.3 mm Hg. The resulting polymer was homogeneous, had a melting 
point of 210.degree. C. and retained good mechanical properties up to 
180.degree. C. 
The properties of the resulting products are reported in the Table which 
follows. 
EXAMPLE 8 
Preparation of polyesteramide based on caprolactam, dimeric acid, poly-THF 
and hexane-1,6-diol 
(1) Preparation of prepolyamide based on caprolactam and dimeric acid: 
A prepolyamide having the following structure was prepared: 
##STR2## 
x is about 8 for a molecular weight of about 1,500. 
The following ingredients were introduced, at ambient temperature, into a 
small glass reactor adopted for operation in vacuo and fitted with a 
stainless steel anchor stirrer: 35.5 g of caprolactam, 3.5 g of 
aminocaproic acid and 14.40 g of dimeric acid. Nitrogen purges were 
carried out and a slow stream of nitrogen was maintained. The temperature 
of the reaction mass was raised to 270.degree. C. (and this temperature 
was maintained for 1 hour 30 minutes, under stirring). A vacuum was then 
established down to about 10 mm of mercury over the course of 30 minutes 
and same was maintained for 10 minutes. The reaction mass was then cooled 
under a stream of nitrogen. 
The resulting prepolymer had a proportion of COOH groups of 1330 meq/Kg and 
a proportion of NH.sub.2 groups which was undetectable by the method 
indicated. 
(2) Preparation of polyesteramide 
20 g of the above prepolyamide, 10 g of poly-THF (TERACOL 1000), 1 g of 
hexane-B 1,6-diol and 10 mg of titanium glycolate were introduced into the 
equipment described above. Nitrogen purges were carried out. The 
temperature of the reaction mass was then raised to 260.degree. C. over 
the course of 40 minutes; a vacuum was established over the course of 45 
minutes until it reached 0.3 mm of mercury, and polycondensation was 
carried out at 260.degree. C. for 1 hour under 0.3 mm of mercury. The 
polyesteramide reached a significant melt viscosity upon completion of the 
reaction and it was transparent and only weakly colored. When cold, the 
polymer was pliable and possessed elastomeric properties. 
The properties of the resulting product are reported in the Table which 
follows. 
EXAMPLE 9 
Preparation of polyesteramide from a prepolyamide with hydroxyl end groups 
and a prepolyester with hydroxyl end groups 
In this example, a polyesteramide composed of 50% by weight of ester units 
and 50% by weight of amide units was prepared from a prepolyamide of 
molecular weight 2,500, which consisted of 50% by weight of a prepolyamide 
of dimeric acid and hexamethylenediamine (HMD) and 50% by weight of a 
prepolyamide of sebacic acid and HMD, and in which the carboxylic acid end 
groups had been esterified with hexane-1,6-diol. The prepolyester had a 
molecular weight of 2,500 and was prepared from dimeric acid and 
hexane-1,6-diol. 
The prepolyamide and the prepolyester of molecular weight 2,000 were 
prepared in a first stage. 
The following ingredients were introduced into a reactor identical to that 
described in Example 6: 
______________________________________ 
Prepolyamide of molecular 
weight 2,500, contain- 
ing OH end groups: 20 g 
Prepolyester of molecular 
weight 2,000, contain- 
ing OH end groups: 20 g 
Hexane-1,6-diol: 1.6 g 
Titanium glycolate: 10 mg 
______________________________________ 
After purges with nitrogen, the temperature of the reaction mass was raised 
to 260.degree. C. over the course of 1 hour, under stirring; same was 
maintained at 260.degree. for 1 hour, a vacuum was then established down 
to 0.45-0.5 mm of mercury and polycondensation was then carried out for 3 
hours under these conditions. The reaction mass obtained upon completion 
of the reaction was very viscous. The product was pliable and homogeneous 
and retained good properties up to 150.degree.-160.degree. C. The 
characteristics are also reported in the Table which follows. 
EXAMPLE 10 
Preparation of polyesteramide (reactants identical to those used in Example 
9, but the percentages of units are different: composition of ester 
units/amide units=75/25 by weight) 
The following ingredients were introduced into a reactor identical to that 
described in Example 6: 
______________________________________ 
Prepolyamide of molecular 
weight 2,500, contain- 
ing OH end groups: 10 g 
Prepolyester of molecular 
weight 2,500, contain- 
ing OH end groups: 30 g 
Hexane-1,6-diol: 1.6 g 
Titanium glycolate: 10 mg 
______________________________________ 
The procedure was identical to that described in Example 9. 
Polycondensation was carried out at 260.degree. C. for 5 hours under 
0.3-0.4 mm Hg. The product was obtained upon completion of the reaction 
was very viscous, pliable and homogeneous and retained good mechanical 
properties up to 120.degree.-130.degree. C. The characteristics are also 
reported in the Table which follows. 
TABLE 
__________________________________________________________________________ 
Inherent 
viscosity in Thermomechanical charac- 
a 0.5% Soften- 
teristics under torsion 
strength ing using an automatic 
solution 
*Thermal charac- 
point 
pendulum 
in m-cresol 
teristics of 
(Kofler Modulus under torsion, 
at 25.degree. C., 
the melting 
bench), MPa 
EXAMPLE 
in dl/g 
endotherms 
.degree.C. 
Tg .degree.C. 
-20.degree. C. 
0.degree. C. 
20.degree. C. 
__________________________________________________________________________ 
1 0.6 not observed 
45-50 
-50 60 32 29 
2 0.71 not observed 
45-50 
-50 10 9 9 
3 0.84 55.degree. C. 
50 -49 8.5 8.3 8 
4 1.18 17.degree. C. 
50-60 
-75 40 23 5.5 
5 1.12 -- 50-60 
-74 40 10 8 
6 not observed 
150-160 
-55 20 15 14 
7 17.degree.C.-210.degree. C. 
180 -44 250 102 65 
8 197.degree. C. 
180 -65 -- -- -- 
9 0.93 217.degree. C. 
150-160 
-59 70 50 40 
10 0.60 120-130 
-59 9 7 6.5 
__________________________________________________________________________ 
*The thermal characteristics are determined by differential 
microcalorimetry under nitrogen, utilizing a temperature increase of 
10.degree. C. per minute. 
While the invention has been describd in terms of various preferred 
embodiments, the skilled artisan will appreciate that various 
modifications, substitutions, omissions, and changes may be made without 
departing from the spirit thereof. Accordingly, it is intended that the 
scope of the present invention be limited solely by the scope of the 
following claims.