y

United States Patent Office 3,287,323

Paterated Nov. 22, 1966
2
3,287.323 lent, based on the said diacid chloride, of meta-phenylene
PROCESS FOR THE PRODUCTION OF A HIGHELY diamine, and (c) an organic, acid accepting diluent which
ORIENTABLE, CRYSTALLIZABLE, FLAMENT
FORMANG POLYAMDE
is a solvent for said diamine and said polyamide and
which is present in such an amount to provide a final
Stephanie Louise Kwolek, Wilmington, Dei., and Paul concentration of 5-35% by weight of polyamide therein,
Winthrop Morgan, West Chester, Pa., assignors to E. H. by addition of said diacid chloride to a solution of said
du Pont de Nemours and Company, Wilmington, Del., diamine in said diluent while maintaining the said con
a corporation of Delaware
No Drawing. Filed Apr. 25, 1963, Ser. No. 275,506 densation mixture under continuous agitation in the ab
1 Claim. (Cl. 260-78) sence of water at a temperature between -20 and 25 C.,
10 preferably 0-25 C., until completion of said addition,
This invention relates to a novel class of crystalline, (2) Continuing said agitation at a temperature not
linear condensation polyamides and to a manufacturing above 30° C. until a polyamide is formed having an in
process therefor. herent viscosity of at least 0.8, and
Among the numerous combinations of bifunctional (3) Separating the polyamide thusly formed.
complementary reactants heretofore suggested for the 15 Strict adherence to the foregoing process variables is
manufacture of linear condensation polyamides, those necessary to obtain the particular polyamides in such
of wholly aliphatic reactants, e.g. adipic acid and hexa form that they be capable of crystallization to a crystal
methylene diamine which yield nylon 66, have been linity index of 50 or more. The reactants and diluent
most frequently employed in commercial practice since should be highly purified such that water and other ex
crystalline products have been readily obtained. Such 20 traneous materials are essentially excluded. The water
crystalline products have been particularly attractive since, content of the reaction mixture, in particular, should not
in comparison with non-crystalline or amorphous forms, exceed 0.02% by weight. For purposes of excluding
they possess higher softening points, distinct melting moisture and other reactive vapors, the reaction should
points, greater light stability and opacity as well as im be conducted under an inert atmosphere such as nitrogen,
proved tenacity and elongation values. 25 dry air or the like. The stoichiometric equivalent of
Although the use of aromatic polyamide reactants is diacid chloride in undiluted form should be added to the
also known, i.e. to achieve other desired benefits, certain diluent solution of diamine as rapidly as possible but
combinations which include such reactants have not previ without permitting the temperature to exceed 25 C.
ously produced Suitable crystalline polymers. Illustrative during the addition. For this purpose it is normally
of such combinations are those of meta-phenylene di 30 desirable to initially cool the diamine solution to a tem
amine and either adipic, suberic or sebacic acid, as de perature between 0 and 10° C. Even after completion
scribed for example in Flory U.S. Patent 2,244,192. of the addition, the reaction mixture should not be
Rather than exhibiting the properties of crystalline poly heated above 30° C.
mers, the products of those materials are amber colored Following complete addition of the diacid chloride to
resinous materials which soften at temperatures con 35 the amine solution it is desirable to allow the reaction
siderably below their melting point. mixture to warm up to between 10 and 25 C. while
In accordance with the present invention, a novel class continuing the agitation for at least 20 minutes. Subse
of crystalline polyamides is provided by means of a unique quently the polycondensate can be precipitated by pouring
series of critical processing steps. In contrast to prior 40 the reaction mixture into water under conditions of
art polyanides prepared to contain the same recurring agitation. The recovered, washed and dried polymer is
units, the products of the invention exhibit the desirable then desirably dry spun from dimethylacetamide or di
features which are generally characteristic of crystalline methylsulfoxide to give fibers with excellent tenacity and
polymers and in addition afford outstandingly higher mod elongation properties.
ulus values. As a consequence of these properties, fabrics Suitable organic, acid accepting diluents in which to
produced of the novel polymers in filament form exhibit 45 conduct the polymerization include alkyl substituted
improved fabric aesthetics. amides such as N-methylpyrrolidone, dimethylacetamide
More particularly the invention provides a linear poly and hexamethyl phosphoramide.
amide Selected from the group consisting of polymeta The manner in which the prepared polyamides are
phenylene adipamide, polymetaphenylene suberamide, and crystallized is not a critical feature of the invention. Al
polymetaphenylene sebacamide, said polyamide having 50 though steam setting of drawn fibers, as performed in the
an inherent viscosity of at least 0.8 and a crystallinity
index above 50. examples, is a preferred technique, others are also suit
able. Typical among such other methods are those in
The novel crystalline polyamides of the invention con Volving dry-heat setting, hot-wet treatment, or the use of
sist of recurring structural units of the formula: hydroxyl-containing organic non-solvent swelling agents,
55 Such as described in U.S. Patents 2,307,846 and 2,289,377.
It is to be understood that once the polymers have
been prepared in a highly purified crystallizable form,
they can be suitably modified as by the inclusion of dyes,
fillers, delusterants, anti-static agents and the like.
60 The crystalline polyamides can be employed in the
wherein m is an even number integer from 4 through 8. form of filaments, sheets, rods, tubes, coatings and the
In filament form, the polyamides have excellent light like. In the form of filaments they are particularly useful
stability and improved tensile properties, particularly in inetc.the fabrication of tire cords, carpets, wearing apparel,
terms of higher modulus and tenacity values.
The method of the invention involves the following 65 Examples I through III hereinafter illustrate the prepa
series of critical steps to obtain a polyamide in a highly ration of polyamides according to the process of the in
orientable, crystallizable form: Vention. Example IV illustrates the crystallization of
(1) Forming an anhydrous condensation mixture con those polyamides in the form of filaments. Example v
sisting of (a) a diacid chloride of an acid selected from demonstrates comparative properties of polymetaphenyl
the group consisting of adipic acid, suberic acid, and 70 ene adipamide versus polyhexamethylene adipamide. In
Sebacic acid, together with (b) a stoichiometric equiva the examples, all parts are by weight unless otherwise
Stated.
pr
3,287,323
3 A.
Example I Example V
In a 500 m. round bottom flask equipped with a stir Highly crystalline yarn samples of the polymetaphenyl
rer was placed 10.814 g. (0.1 mole) m-phenylenedi ene adipamide of Example I and commercial polyhexa
amine and 75 ml. dimethylacetamide. The solution was methylene adipamide, respectively, were exposed to ultra
cooled with ice to 10° C. From a pipette there was violet light irradiation for purposes of measuring the
added rapidly 14.7 ml. (0.1 mole) of adipyl chloride. attendant degradation in terms of tenacity-elongation
The flask was cooled continuously with ice and the con half-life. The results are significantly in favor of poly
tents vigorously stirred while the temperature of the re metaphenylene adipamide, which has a tenacity-elonga
action was maintained below 25 C. Following addition O
tion half-life of 450 hours as compared to polyhexameth
of the adipyl chloride, the viscous mixture was stirred ylene adipamide which has a tenacity-elongation half
for one hour without allowing the temperature to exceed life of only 185 hours.
25° C. The polymer was precipitated by adding water, For the preparation of the polyamides in Examples I,
washed several times with water and once with an ethyl II and III, extreme care was exercised to ensure that
alcohol/water mixture (1/1 by volume). Polymeta 5 the condensation reactions proceeded in the absence of
phenylene adipamide having a polymer melting tem impurities which might have prevented the formation of
perature of 344° C. and an inherent viscosity of 1.66 crystallizable polymers. For this reason the dimethyl
in m-cresol was produced in a yield of 100% of that acetamide employed was distilled from m-tolylene diiso
theoretically obtainable. cyanate through a spinning band column under reduced
Example II 20 pressure. The adipyl chloride was distilled through a
Vigreux column under very low vacuum. Suberyl chlo
In a 500 m. round bottom flask equipped with a stir ride was prepared from suberic acid and thionyl chlo
rer was placed 2.163 g (0.020 mole) m-phenylene di ride and fractionally distilled under vacuum. Sebacyl
amine and 18 m. dimethylacetamide. The solution was chloride was purified by fractional distillation under re
cooled with ice to 10° C. and 4.22 g. (0.020 mole) 25 duced pressure. The reagents thus prepared and highly
suberyl chloride added rapidly from a pipette while cool purified were absolutely dry. Only the solvent dimethyl
ing and stirring to maintain the temperature constantly acetamide contained a trace of water and that never
below 25° C. The mixture was thereafter stirred for exceeded 0.02%. All condensations were performed un
one additional hour at the same temperature. Finally der an atmosphere of dry nitrogen in order to exclude
the polymer was precipitated with water in a Waring 30 moisture.
Blendor and washed with water and an ethyl alcohol/ All values of inherent viscosity in the specification and
water mixture (1/1 by volume). Polymetaphenyiene claim were calculated from the equation:
suberamide, polymer melting temperature 302 C. and
inherent viscosity of 1.42 in m-cresol, was obtained in
100% yield as a white granular material. Inherent viscosity
Example III
In a 500 ml. round bottom flask equipped with a stir wherein R is the viscosity of a solution of 0.5 gram of
rer was dissolved 2.163 g. (0.020 mole) m-phenylene di the polymer in 100 milliliters of solvent at 30° C. divided
amine in 18 ml. dimethylacetamide. The solution was by the viscosity of the solvent in the same units and at
cooled to 10° C. and thereafter 4.27 ml. (0.020 mole) 40 the same temperature, and C is the concentration of
sebacyl chloride were added rapidly from a pipette. The the polymer solution in grams of polymer per 100 milli
cooling was continued and the temperature of the re liters of solution. For purposes of this invention, m
cresol is the solvent.
action maintained below 25 C. After stirring for 1. The polymer melting temperatures given in the exam
hour the polymer was precipitated with water in a Waring
Blendor. It was washed with water and an ethyl al 45 ples are determined by passing a stick of solid polymer
cohol/water mixture (1/1 by volume) several times. in sliding contact with a heated metal bar. The bar tem
Granular, white polymetaphenylene sebacamide was ob perature at which a streak of molten polymer is initially
tained in 100% yield. Melting temperature of the poly formed is taken as the polymer melting temperature.
mer was 258 C. Inherent viscosity in m-cresol was The values of crystallinity index referred to herein are
1.20. 50 measured according to the procedure of Wakelin, Virgin,
Example IV and Crystal, Journal of Applied Physics, vol. 30, pages
1654-1662 (1959). According to this procedure the -
The polymetaphenylene adipamide, polymetaphenylene most crystalline soluble polymer sample obtainable is
suberamide and polymetaphenylene sebacamide of EX given a value of 100 and the least crystalline sample a
amples I to III, respectively, were dissolved in dimethyl value of zero. The index for the various fiber samples
acetamide to a 30% solution. The solution was dry is thus a relative measure of crystallinity between these
spun into the form of a yarn by forcing the solution two known extremes. To obtain the zero index for the
through a spinneret into a long chamber, kept at 190 polymers disclosed herein the latter were spun into fibers
C., to evaporate the solvent. The amorphous yarn with which were wholly amorphous as determined by X-ray
0 crystallinity index was then drawn and collected on 60 analysis. To obtain the 100 index a melt pressed film
a metal bobbin. The yarn of polymetaphenylene adip was allowed to soak in an aqueous 50% dimethylforms
amide had a T/E/M (tenacity, elongation, initial mod amide Solution for 10 minutes and then thermally an
ulus) of 5.4/31/75, the T/E value for polymetaphenyl nealed for six hours at 200 C.
ene suberamide was 1.27/17, and that for polymeta Values of tenacity and elongation given in the exam
phenylene sebacamide was 1.95/198. 65 ples are in units respectively of grams/denier and per
The metal bobbin with the fiber was then placed in cent and are determined in the conventional manner.
a steam autoclave, the steam pressure regulator set to Initial modulus values are determined as described in
50 p.s. i. and the fiber exposed to this pressure at a tem U.S. Patent 2,956,330, column 7.
perature of 147.6° C. for between 30 and 45 minutes. What is claimed is:
Upon release of the steam, the fibers were allowed to 70 Method for the production of a highly orientable, crys
cool at room temperature. The crystallinity index of tallizable, filament-forming polyamide, said method com
the treated fibers was as follows: prising the steps of
above 75 for polymetaphenylene adipamide, (1) forming an anhydrous condensation mixture con
between 50 and 60 for polymetaphenylene suberamide, sisting of (a) a diacid chloride of an acid selected
between 50 and 60 for polymetaphenylene Sebacamide. 75 from the group consisting of adipic acid, suberic
 8,287,323
5 6
acid and sebacic acid, together with (b) a stoichio References Cited by the Examiner
metric equivalent, based on the said diacid chloride, UNITED STATES PATENTS
of meta-phenylene diamine, and (c) an organic,
acid accepting diluent selected from the group con 2,244,192 6/1941 Flory --------------- 260-78
sisting of N-methylpyrrollidone, dimethylacetamide 2,336,384 12/1943 Baker et al. ---------- 260-78
and hexamethylphosphoramide and which is pres 2,352,725 7/1944 Markwood ---------- 260- 78
ent in such an amount to provide a final concentra 2,831,834 4/1958 Magat -------------- 260- 78
tion of 5-35% by weight of polyamide therein, said 2,880,057 3/1959 Cuculo -------------- 260-78
mixture being formed by addition of said diacid chlo 3,063,966 11/1962 Kwolek et al. -------- 260-78
ride to a solution of said diamine in said diluent O 3,143,528 8/1964 Finestone et al. ------- 260-78
while maintaining the said condensation mixture un FOREIGN PATENTS
der continuous agitation in the absence of oxygen
at a temperature between -20 and 25 C. until com 614,625 12/1948 Great Britain.
pletion of said addition, OTHER REFERENCES
(2) continuing said agitation in the absence of water 15 Mark et al., Physical Chemistry of High Polymeric
and at a temperature not above 30° C. until a poly Systems, Interscience, N.Y., 1950, pp. 357-359, 363.
amide is formed having an inherent viscosity of at Tobalsky, Properties and Structure of Polymers, John
least 0.8, as measured at 30° C. in m-cresol solvent Wiley and Sons, N.Y., 1960, p. 198.
at a concentration of 0.5 gram polymer per 100 ml.
solvent, and 20 WILLIAM. H. SHORT, Primary Examiner.
(3) separating the polyamide thusly formed. H. D. ANDERSON, Assistant Examiner.