Polyamide reaction products comprising: a dicarboxylic acid and a diamine component comprising a mixture of poly(oxytetramethylene) diamines and oligomers of said poly(oxytetramethylene) diamines, PA1 said mixture containing from about 85 to about 99.5 wt. % of said poly(oxytetramethylene) diamines and, correspondingly, from about 15 to about 0.5 wt. % of said oligomers, PA1 said poly(oxytetramethylene) diamines having the formula: ##STR1## wherein n represents 0 or a positive number having a value of 1 to about 30, PA1 said oligomers having the formula: ##STR2## wherein n represents 0 or a positive number having a value of 1 to about 30.

BACKGROUND OF THE INVENTION 
1. Technical Field of the Invention 
This invention relates to thermoplastic thermosettable polyamides having 
enhanced low temperature flexibility and high temperature thermal 
stability properties. More particularly, this invention relates to 
modified polyamides that are essentially linear and thermoplastic at 
temperatures of less than about 250.degree. C. and thermosetable at 
temperatures of about 250.degree. C. or more (e.g., 260.degree. to 
300.degree. C.); such polyamides being useful in the formation of fibers, 
molded parts, hot melt adhesives, etc. Still more particularly, this 
invention relates to polyamides modified by the inclusion therein of 
mixtures of poly(oxytetramethylene) diprimary amines with 
poly(oxytetramethylene) oligomers containing one or more internal 
secondary amine groups and terminal primary amine groups. 
2. Prior Art 
Poly(oxytetramethylene) diprimary amine oligomers containing internal 
secondary amine groups are disclosed in Schoenieben et al. European Patent 
No. 0,354,501 dated Jun. 8, 1989. 
Nakagawa et al. U.S. Pat. No. 3,558,419 is directed to composite filaments 
and fibers wherein one of the components is a polyalkylene 
ether-polyamide-block copolymer containing linear polyamide segments and 
polyoxyalkylene ether segments. Amine derivatives of polyoxyethylene 
glycols, when incorporated into polyamides, tend to affect the water 
solubility characteristics of the resultant polyamides. 
In Yeakey et al. U.S. Pat. No. 4,128,525, thermoplastic adhesive components 
are disclosed which are prepared from a polyoxypropylene polyamine, 
piperazine and a dicarboxylic acid. 
Linear polymeric amines prepared by first propoxylating a 
poly(oxytetramethylene) glycol and then reductively aminating the adduct 
are disclosed in Watts, Jr. et al. U.S. Pat. No. 4,181,682. 
Rasmussen U.S. Pat. No. 4,218,351 is directed to impact resistant 
thermoplastic polyamides composed of a short chain polyamide-forming 
moiety, a polyamide-forming dimer acid moiety and a polyamide-forming 
oligomer moiety. 
Wettable adhesives comprising a mixture of polyvinyl alcohol and a water 
soluble polyamide are disclosed in Soerens U.S. Pat. No. 4,684,439. The 
polyamide comprises a reaction product of a polyoxyalkylene polyamine, a 
saturated aliphatic dicarboxylic acid and a polyalkylene polyamine. 
Mitchell et al. U.S. Pat. No. 4,062,820 is directed to hot melt adhesives 
prepared by the co-condensation of stoichiometric amounts of (a) a mixture 
of a polymeric fatty acid and a saturated aliphatic dicarboxylic acid with 
(b) a mixture of a saturated aliphatic diamine with either a 
polyoxyethylene diamine or a polyoxypropylene diamine. 
Resinous polyoxamide thermoplastic adhesive compositions are disclosed in 
Schulze U.S. Pat. No. 4,119,615 that are prepared by reacting a 
polyoxypropylene diamine or a polyoxypropylene triamine with oxalic acid 
or a dialkyl ester of oxalic acid to prepare a liquid prepolymer that is 
then reacted with a diamine to provide the resinous polyoxamide. 
Resinous thermoplastic adhesive compositions are disclosed in Klein U.S. 
Pat. No. 4,133,803 that are prepared by reacting a polyoxypropylene 
diamine or a polyoxypropylene triamine, such as ethylene diamine, with an 
aromatic or aliphatic dicarboxylic acid or an ester or anhydride thereof, 
such as isophthalic acid, dimethyl terephthalate or phthalic anhydride. 
Vogel U.S. Pat. No. 4,151,173 discloses lubricating oil additives prepared 
by reacting a polyoxyalkylene polyamine, such as a polyoxypropylene 
diamine or a polyoxypropylene triamine with a carboxylic acid acylating 
agent such as a polyisobutenyl succinic anhydride. 
Thermoplastic adhesive compositions are disclosed in Yeakey et al. U.S. 
Pat. No. 4,162,931 and Yeakey et al. U.S. Pat. No. 4,182,845 that are 
prepared by reacting a polyoxypropylene diamine or a polyoxypropylene 
triamine with piperazine and an aromatic or aliphatic dicarboxylic acid or 
an ester or anhydride thereof, such as isophthalic acid. 
Rieder U.S. Pat. No. 4,239,635 discloses carboxylic acid terminated 
diamides, and the alkali metal, ammonium and amine salts thereof prepared 
by reacting an excess of a polyoxyalkylene polyamine, such as a 
polyoxypropylene diamine with an excess of an organic polycarboxylic acid. 
Hot melt adhesive copolyamide compositions are disclosed in Sharkey U.S. 
Pat. No. 4,282,346 that are prepared by reacting a polyoxypropylene 
diamine with piperazine and mixture of a long-chain and a short-chain 
saturated aliphatic dicarboxylic acid such as adipic acid and azelaic 
acid. 
See also, Vol. 18, pp. 328-436 of the Encyclopedia of Chemical Technology, 
Kirk Othmer, 3rd Edition. 
Newbould in an article entitled "Controlling Melt Viscosity of High Melting 
Point Polyamides" (Adhesives Age, November 1986, pp. 24-29) discusses 
polyamide-type hot melt adhesives such as those prepared from 
hexamethylene diamine, adipic acid, azelaic acid or dimer acids. 
Iwabuchi et al. in a paper entitled "Preparation of Regularly Sequenced 
Polyamides with Definite Numbers of Oxyethylene Units and Their 
Application as Phase Transfer Catalysts" (Makromol. Chem., Vol. 184, pp. 
535-543 (1983)) disclose polyamides having oligo(oxyethylene) segments 
prepared from alpha-(2-aminoethyl)-omega-aminooligo(oxyethylenes) and 
dicarboxylic acid chlorides. 
BACKGROUND INFORMATION 
As exemplified by the prior art mentioned above, polyamides formed by the 
polymerization of amino acids or the co-condensation of aliphatic diamines 
with dicarboxylic acids, and frequently referred to as "nylons" or 
nylon-type materials, are useful for a variety of purposes, including film 
and fiber preparation, the formation of molded parts, the preparation of 
hot melt adhesives, etc. The results obtained through the use of such 
materials have generally been satisfactory, but there is need for 
improvement. 
SUMMARY OF THE INVENTION 
This invention relates to polyamides modified by the inclusion therein of a 
mixture of poly(oxytetramethylene) diamines and oligomers thereof that are 
useful in the formation of fibers, molded parts, hot melt adhesives, etc., 
such poly(oxytetramethylene) diamines having the following formulas: 
##STR3## 
wherein n represents 0 or a positive number having a value of 1 to about 
30, and 
the oligomers have the formula: 
##STR4## 
wherein n represents 0 or a positive number having a value of 1 to about 
30. 
In copending Speranza et al. application Ser. No. entitled "Modified 
Polyamides having Improved Thermal Stability", filed of an even date 
herewith, it is disclosed that improved flexibility can be imparted to 
polyamides when the polyamides are modified by the incorporation therein 
of a poly(oxytetramethylene) diamine having the formula: 
##STR5## 
wherein n represents 0 or a positive number having a value of 1 to about 
30. 
In accordance with the present invention the physical properties, including 
low temperature properties of polyamides, are still further improved 
through the further incorporation into polyamides of 
poly(oxytetramethylene) diamine oligomers having the formula: 
##STR6## 
wherein n represents 0 or a positive number having a value of 1 to about 
30.

DETAILED DESCRIPTION 
The polyamide-modifying starting materials for the present invention are 
poly(oxytetramethylene) diamines having the formulas: 
##STR7## 
wherein n represents 0 or a positive number having a value of 1 to about 
30, and oligomers thereof having the formula: 
##STR8## 
wherein n represents 0 or a positive number having a value of 1 to about 
30. 
The starting materials for the preparation of polyamides include 
dicarboxylic acids, such as those selected from the group consisting of 
alkane dicarboxylic acids containing 6 to 12 carbon atoms and 
unsubstituted or C.sub.1 -C.sub.4 alkyl substituted benzene dicarboxylic 
acids, saturated aliphatic amino acids containing 6 to 12 carbon atoms, 
saturated aliphatic lactams containing 6 to 12 carbon atoms, and saturated 
aliphatic diamines containing 2 to 12 carbon atoms. 
The Poly(oxytetramethylene) Diamines 
The poly(oxytetramethylene) diamine starting materials to be used in 
accordance with the present invention can be prepared by the process 
disclosed in copending Larken et al. U.S. patent application Ser. No. 
07/452,146, filed Dec. 18, 1989, and entitled "Improved Catalytic Method 
for the Reductive Amination of Poly(oxytetramethylene) Glycols". 
Diamines having molecular weights of about 250, 650, 1,000 and 2,000 can be 
obtained from poly(oxytetramethylene) glycols through the use of the 
process disclosed in Larken et al. copending application Ser. No. 
07/452,146, filed Dec. 18, 1989, by bringing a poly(oxytetramethylene) 
glycol into contact with an appropriate nickel, copper, molybdenum, 
chromium catalyst in the presence of from about 1 to 300 moles of ammonia 
per mole of poly(oxytetramethylene) glycol and about 0.1 to 10 moles of 
hydrogen per mole of poly(oxytetramethylene) glycol under suitable 
reductive amination conditions, including a temperature of about 
150.degree. to about 220.degree. C., a pressure of about 100 to about 
10,000 psig and a reaction time of about 0.5 to 5 hours. 
The practice of this process will result in the substantial conversion of 
the terminal hydroxyl groups of the glycol to terminal primary amine 
groups. 
At comparatively high reductive amination conversion levels, such as 
conversion levels of more than about 90% of the poly(oxytetramethylene) 
glycol, a minor amount of the conversion reaction product (e.g., about 5% 
or less) will contain secondary amine groups, such as secondary amines 
having the formula: 
##STR9## 
wherein n has a value of 0 to about 30. 
At lower reductive amination conversion levels of about 50% or less, the 
formation of secondary amine groups is insignificant. 
In the practice of the present invention it is necessary to use both of the 
primary diamine products of formula I and oligomers of formula II. This 
can be accomplished by conducting the reaction at a comparatively high 
conversion level of about 90% or more. 
The oligomers can also be prepared by the process disclosed in Schoenieben 
et al. European Patent No. 0,354,501. 
POLYAMIDE PREATION 
The Dicarboxylic Acid Starting Materials 
The dicarboxylic acids to be used in the preparation of polyamides are of 
the type known to those skilled in the art, such as dicarboxylic acids 
selected from the group consisting of alkane dicarboxylic acids containing 
6 to 12 carbon atoms and unsubstituted or alkyl substituted benzene 
dicarboxylic acids. 
Suitable saturated aliphatic dicarboxylic acids that may be used include 
compounds such as adipic acid, pimelic acid, suberic acid, azelaic acid, 
sebacic acid, dodecane-dioic acid, etc., and mixtures thereof. 
Suitable unsubstituted or C.sub.1 -C.sub.4 alkyl substituted benzene 
dicarboxylic acids that may be used include compounds such as benzene 
dicarboxylic acids, isophthalic acid, terephthalic acid, etc., and 
mixtures thereof. 
The Saturated Aliphatic Amino Acid Starting Materials 
Representative saturated aliphatic amino acid starting materials include 
amino acids containing 6 to 12 carbon atoms. 
Examples of amino acids that may be used are compounds such as 
6-aminocaproic acid, 11-amino-undecaneoic acid, etc., and mixtures 
thereof. 
The Saturated Lactam Starting Materials 
The saturated aliphatic lactams that may be used as starting materials are 
saturated lactams containing 6 to 12 carbon atoms, 
Lactams such as epsilon caprolactam, enantholactam, capryllactam, 
undecanolactam, laurylactam and alkyl substituted caprolactams, etc., and 
mixtures thereof may be used. The preferred starting material is epsilon 
caprolactam. 
The Aliphatic Diamine Starting Materials 
Representative saturated aliphatic diamines that may be used as starting 
materials are saturated aliphatic diamines containing 2 to 12 carbon 
atoms, such as ethylene diamine, tetramethylenediamine, 
hexamethylenediamine, dodecamethylenediamine, piperazine, 2,5-dimethyl 
piperazine, diaminocyclohexane, etc. 
Preferred Embodiments 
In accordance with the present invention, a mixture of the 
poly(oxytetramethylene) diamine of formula I with oligomers of formula II 
is prepared for incorporation into a polyamide, such mixture containing 
from about 0.1 to about 15 wt. % of the oligomers. When the mixture is to 
be incorporated into a polyamide to be used for the preparation fibers, it 
is preferred that the mixture contain from about 0.1 to about 10 wt. % of 
the oligomers. When molded articles or hot melt adhesives are to be 
prepared, the mixture will suitably contain from about 1 to about 10 wt. % 
of the oligomers. 
In accordance with one preferred embodiment of the present invention, a 
polyamide is prepared by reacting an equimolar amount of a dicarboxylic 
acid component with a diamine component consisting of a mixture of the 
poly(oxytetramethylene) diamines of formula I with oligomers of formula II 
and the two components are then mixed and reacted in accordance with known 
polyamide-forming procedures to prepare a polyamide co-condensation 
product. 
In general, such polyamide co-condensation products are characterized by 
good color, good low temperature stability and good flexibility. The 
co-condensation products can also be used to prepare fibers, films, molded 
products, adhesives, etc. 
In accordance with another preferred embodiment of the present invention, a 
polyamide is prepared from a first component composed of equimolar 
portions of a poly(oxytetramethylene) diamine and oligomers thereof and a 
dicarboxylic acid and a second component composed of equimolar amounts of 
a saturated aliphatic diamine containing 2 to about 12 carbon atoms and a 
dicarboxylic acid, as defined above. In accordance with this embodiment, 
the first component may be used in the form of a salt of a 
poly(oxytetramethylene) diamine or oligomer with a dicarboxylic acid which 
is reacted with the second component, and the second component may also be 
used in the form of an aliphatic diamine salt of a dicarboxylic acid. 
Alternately, the aliphatic diamine, the poly(oxytetramethylene) diamine 
and the dicarboxylic acid can be used in monomeric form and co-reacted in 
a single reaction step. 
As a third alternative, the first components can be co-reacted to form a 
first co-polyamide, the second components can be reacted to form a second 
co-polyamide and the first co-polyamide can then be blended with the 
second co-polyamide to form a polyblend. 
In accordance with this preferred embodiment, the final polyamide 
co-condensation product will be composed, preferably, of about 5 to about 
100 wt. % of the first components and, correspondingly, from about 95 to 
about 0 wt. % of the second components. The final polyamide 
co-condensation products are characterized, in general, as having good 
thermostability properties, good flexibility properties and improved 
toughness. They may be used, for example, to prepare films, fibers, molded 
products and elastomers. 
In accordance with a third preferred embodiment, a co-polyamide 
co-condensation product is prepared from a first component composed of 
equimolar portions of a dicarboxylic acid and poly(oxytetramethylene) 
diamines and oligomers thereof and a second component composed of a 
saturated aliphatic lactam containing 6 to 12 carbon atoms. Again, the 
first component may be used in the form of a salt of a 
poly(oxytetramethylene) diamine with a dicarboxylic acid which is 
coreacted with the second component, or the components may be used as 
monomers and co-condensed. The final polyamide co-condensation product 
will be composed, preferably, of about 5 to about 100 wt. % of the first 
components and, correspondingly, from about 95 to about 0 wt. % of the 
second component. The final polyamide co-condensation products are 
characterized, in general, as having good thermostability properties, good 
flexibility properties and improved toughness. They may be used, for 
example, to prepare fibers, and elastomers. 
In accordance with a fourth preferred embodiment of the present invention, 
a co-polyamide co-condensation product is prepared from a first component 
composed of equimolar portions of a dicarboxylic acid and 
poly(oxytetramethylene) diamines and oligomers thereof and a second 
component composed of a saturated aliphatic amino acid containing 6 to 
about 12 carbon atoms. As previously indicated, the first component may be 
used in the form of a salt of a poly(oxytetramethylene) diamine with a 
dicarboxylic acid and may be co-reacted with the second component, or the 
components may be used as monomers and co-condensed. The final polyamide 
co-condensation product will be composed, preferably, of about 5 to about 
100 wt. % of the first components and, correspondingly, from about 95 to 
about 0 wt. % of the second component. The final polyamide co-condensation 
products are characterized, in general, as having good thermostability 
properties, good flexibility properties and improved toughness. They may 
be used, for example, to prepare fibers, and elastomers. 
Reaction Conditions 
The reactants are copolymerized under conventional reaction conditions in a 
reactor provided with suitable temperature control means and suitable 
agitation means at a temperature, for example, within the range of about 
150.degree. to about 300.degree. C. for a reaction time within the range 
of about 2 to about 10 hours. A catalyst is not required. An oxidation 
inhibitor may be included in the reaction mixture to prevent oxidated 
deterioration of the reaction product. Suitable oxidation inhibitors 
include materials such as Ultranox 246, Irganox 1010, Irganox 1098, 
Irganox 1171, Irgafos 168 and mixtures thereof. 
Thermosetability 
The polyamide products of the present invention, as prepared, are 
thermoplastic materials that may be formed into desired final products 
such as hot-melt adhesives, moldings, films and fibers by known polyamide 
utilization procedures and may also be modified, in accordance with known 
technology, by the incorporation therein of other components such as 
conventional polyamides or other polymers and additives such as fillers, 
dyes, oxidation inhibitors, etc. 
The polyamides of the present invention will remain thermoplastic at 
temperatures of about 250.degree. C. or less. However, if the polyamides 
are heated to higher temperatures, cross-linking may occur, at least to a 
limited extent. 
In accordance with a further preferred embodiment of the present invention, 
this unusual property is deliberately utilized by forming the 
thermoplastic polyamide into a desired form at a temperature of less than 
about 250.degree. C. and by then heating the formed polyamide to a 
thermosetting temperature, such as a temperature of about 260.degree. to 
about 300.degree. C., preferably in an inert atmosphere, for about 0.1 to 
about 10 hours to thermoset the polyamide and thereby enhance the rigidity 
of the polyamide. 
In the conversion of alcohols to amines by the action of ammonia over a 
metal catalyst primary, secondary and tertiary amines may form. 
##STR10## 
The reaction using secondary alcohols is more selective and less secondary 
and tertiary amines are formed. 
##STR11## 
To convert diprimary glycols to diamines is very difficult. In the 
aminolysis of polytetrahydrofuran there is always some triamine formed 
when the reaction is carried out to high conversion. 
##STR12## 
It would be very desirable to use these amines because they have polyether 
groups which are more heat stable than conventional polyether polyamines. 
For example, when adipic acid was heated with products containing A and B, 
where x is greater than 2, colorless crosslinked polymers were obtained 
that were heat stable at 283.degree. C. under nitrogen. When this amine 
mixture was heated with sebacic acid or terephthalic acid, under the same 
conditions as that used in the adipic reaction, soft weak elastomeric 
fibers would be obtained. It was not until the reaction was carried out at 
280.degree. C. and 0.2 mm did we obtain the expected crosslinked polymer. 
Thus, the diamines mixed with the triamines have the potential of being 
important in the preparation of thermoset polymers. For adhesive 
applications, the polyamidation might be carried out to only a partial 
extent and then cured at a later stage. 
A clear use for these compounds are as tackifying additives for adhesives 
when used in conjunction with other dicarboxylic acids such as diamido 
acids. One product from the 1000 molecular weight polyol in which a high 
secondary amine content was made on purpose was studied (amine A+B). 
__________________________________________________________________________ 
NH.sub.2 --(CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 O).sub.13 --CH.sub.2 
CH.sub.2 CH.sub.2 CH.sub.2 --NH--(CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 
O).sub.13 --CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 NH.sub.2 + Diamine 
Total Amine 1.6 meq/g Primary amine 1.20 meq/g 
Acid, moles 
Amine A + B, moles Amine, moles Remarks 
__________________________________________________________________________ 
adipic, 1 1 -- Hard, tough, elastic, 
transparent, not liquid 
at 250.degree. C. 
dimer, 1 1 -- Tough, elastic, trans- 
parent, not liquid at 
250.degree. C. 
adipic, 1 0.1 triethylene Tough, hard, opaque 
glycol diamine, 
molten at 190.degree. C. 
0.9 
dimer, 1 0.5 ethylenediamine*, 
Pliable solid, not 
0.5 liquid at 250.degree. C. 
adipic, 1 0.1 hexamethylene- 
Hard, opaque, softens 
diamine, 0.9 at about 150.degree. C., waxy 
at 250.degree. C. 
__________________________________________________________________________ 
*The ethylenediamine and dimer acid were prereacted before reaction with 
amine A + B. 
When compounds A and B are both mixed with dicarboxylic acids such as 
adipic and sebacic at 260.degree.-300.degree. C., crosslinked polymers are 
formed. The degree of crosslinking depends on the amount of B. If B is 
present in small amounts and these components are mixed with dicarboxylic 
acids and caprolactam, adipic acid, hexamethylene diamine, amino acids, 
its polyamides are formed which can be melt spun into fibers or molded. In 
such cases the concentration of A is much greater than B and the 
combination of A and B represents a minor portion of the amino fraction of 
the polymer--up to about 30% if the proportion of A to B is very high. 
The advantage of using the polyether amines described in this invention is 
that they are heat stable amines which impart flexibility to the 
polyamides. For example, similar compounds such as C and D are less color 
stable when heated to 280.degree. C. with adipic acid (x is 0, 1, 2, 3, 
etc.). 
##STR13## 
As an example, compounds such as C and D start to turn light yellow when 
heated with a molar amount of adipic acid under nitrogen at 250.degree. C. 
A mixture containing A and B when heated with a molar amount of adipic 
acid remained colorless when heated to 283.degree. C. under nitrogen. 
The introduction of a small amount of a triamine can be beneficial to the 
process of polyamine formation (see U.S. Pat. No. 4,906,783 and references 
therein). The triamine used in our work also adds impact strength to the 
polyamides. 
EXAMPLES 
The present invention will be further illustrated by the following specific 
examples which are given by way of illustration and which are not intended 
as limitations on the scope of this invention. 
EXAMPLE 1 
Examples 1 and 2 utilize a poly(oxytetramethylene) diamine (6374-61-1) 
which had the following analysis: 
Total acetylatables 1.952 meq/g 
Amine assay 1.838 meq/g 
Primary amine 1.729 meq/g 
It is estimated that product was about 94% amine with about 94% of the 
amine being primary diamines. Water (2.0 parts), 0.62 parts 6374-61-1, 
0.083 parts of adipic acid and 3.616 parts of caprolactam was heated at 
270.degree.-280.degree. C. for five hours. Excellent fibers were pulled 
from the melted polymer. 
EXAMPLE 2 
Water (1.5 parts), 3.87 parts caprolactam, 0.58 parts 6374-61-1 and sebacic 
acid were heated at 270-290.degree. C. for five hours. Nice fibers were 
obtained. 
EXAMPLE 3 
Terephthalic acid (1.66 parts), 2.36 parts 6600-53-7 
(diaminotri-1,4-butylene glycol), and 0.5 parts of water were heated at 
280.degree. C. for three hours and then at 280.degree. C. for 3 hours at 
0.3 mm. (Purified nitrogen was passed through the contents in this and all 
experiments described.) Fibers were obtained, although somewhat brittle 
indicating higher temperatures may be required. 
EXAMPLE 4 
Examples 4 and 5 utilize a poly(oxytetramethylene) 6374-77-3 which had the 
following analysis: 
Total acetylatables 2.71 meq/g 
Total amine 2.60 meq/g (95%) 
Primary amine 2.40 meq/g (92%) 
In a small reactor was heated 3.1 parts of 6374-77-3 and 0.56 parts of 
adipic acid and the contents heated at 280.degree. C. for four hours. An 
off-white, transparent, elastomeric product was obtained. A steel ball did 
not penetrate the polymer at 280.degree. C., which indicated that 
crosslinking had taken place. Thermogravimetric analysis showed a weight 
loss of only 0.3% at 300.degree. C. and 1.0% loss at 350.degree. C. when 
heated under nitrogen. 
EXAMPLE 5 
Sample 6374-77-3 (3.04 parts) was heated with 0.77 parts of sebacic acid 
for four hours at 260.degree. C. At this point nice, long fibers could be 
pulled from the sample and the product melted at 60.degree. C. The sample 
was then heated at 280.degree. C. and 0.2 mm pressure for three hours. The 
product was a hard, rubbery rock which stuck to glass. 
EXAMPLE 6 
Polyamine 6374-61-1 (3.57 parts) was heated with 0.76 parts of dodecanedioc 
acid at 260.degree. C. for 3.5 hours. The product melted at 80.degree. C. 
and was colorless, hard elastomer. It showed 1% weight loss at 350.degree. 
C. when heated for 10 minutes at 350.degree. C. under nitrogen. When a 
steel ball was placed on the sample in a tube and the contents heated to 
282.degree. C., the ball sank only part of the way indicating crosslinking 
was taking place at the higher temperature. 
EXAMPLE 7 
When 0.48 parts of terephthalic acid were heated with 3.15 parts of 
6374-61-1 for four hours at 260.degree. C., and at 280.degree. C. for 
three hours under vacuum, fairly strong elastic fibers could be pulled 
from the molten mass. This experiment demonstrates that aliphatic dibasic 
acids increase the rate of the crosslinking step over aromatic dibasic 
acids. 
In Examples 1-7 we have shown how fibers may be formed and how high 
molecular weight tough thermoset elastomeric polyamine adhesives can be 
made. Additional flexibility can be added by the addition of dimer acid. 
Other modifications can be made by the addition of other amines. 
Essentially, all of the formulations led to flexible adhesive-type 
products except those where some incompatibility resulted. In such 
formulations, the products were usually hard and opaque.