I

RENE AELION
Research and Development Laboratory, Foster Grant Co., Inc., Leominster, Mass.

Nylon 6 and Related Polymers

M a n y higher nylon polymers have interesting and useful properties, but r a w material
costs and ease of production will be the key factors in determining volume production
existing differences are due mainly to
the physical and chemical properties of
the monomers and the effects they have
on the polymerization process.
The principal factor is the production
cost of the monomer. In this respect,
the anticipated expansion of the production of caprolactam arising from a
downward trend in processing costs
should give a definite advantage to
nylon 6 over the others for large scale
development.

I N THE LINEAR ALIPHATIC POLYAMIDE

field, four types of nylon have been produced on a large industrial scale for
more than 10 years. Two of them,
nylon 6,6 and nylon 6,10, are prepared
from a diacid, diamine salt formulation:
HJiCH2)6NH*, HOOC(CH2)aCOOH
+ nylon 6.6
H,N-(CH~)G-NH~,
HOOC-(CHt),-COOH
-+ nylon 6,lO
and the others, nylon 6 and nylon 11,
from a lactam and an amino acid :
HN(CH2)s-CO
L

-+

R a w Materials

nylon 6

A general method for the synthesis of

lactams has been developed. The starting material is a cyclic hydrocarbon
with one less atom in the ring than exists
in the corresponding lactam. A ketone
group is fixed on this ring (Q), then the
nitrogen atom is introduced by oximation (7), and the lactam group is
formed by the Beckmann rearrangement

H1N-(CH,)lo-COOH -+ nylon 11
In each class one member has a short
aliphatic chain and the other member a
much longer one. These four basic
types of nylon already cover a relatively
wide range of properties.
I n recent years, extensive research in
several countries has been carried out to
determine if these four types of nylon
were the only ones presenting interesting
commercial applications, either in the
plastic or in the textile fields. Other
types of nylon, mainly prepared from
amino acid and lactams, were investigated from the standpoints of costs and
properties in comparison with those
already produced. A few have reached
a pilot plant evaluation, and it has been
found that their properties, although
interesting, vary within the limits set
up by the four basic nylons.
The

(4

For caprolactam the commonly employed raw materials are benzene,

phenol, and cyclohexane. I n the case
of the higher lactams listed (below), an
additional step is required to obtain
first the 8- and 12-membered ring materials which are not readily available.
I n the case of caprylactam, this ring is
obtained either by polymerization of 4
molecules of acetylene (6) or by the
dimerization of butadiene (70). I n
a similar way, the 12-member ring for
the preparation of dodecalactam can

Monomers Used in the Preparation of Nylons

Formulas

Monomer

Valerolactam

Nylon Types

HN-(CH2)4CO

Nylon 5

L--I

Caprolactam

HN-(CH2)5CO
I

7-Aminoheptanoic acEd
Caprylactam

H2N-(CH2)6COOH
HN-(CHz,)vCO
L

9-Aminopelargonic acid
1 1-Aminoundecanoic acid
Dodeca lacta m

826

Nylon 6

H2N-(CH2)sCOOH
H2N-(CHz)laCOOH
HN-(CHz)11CO
I
J

INDUSTRIAL AND ENGINEERING CHEMISTRY

Nylon 7
Nylon 8
Nylon 9
Nylon 1 1
Nylon 12

be obtained by trimerization of butadiene (70). The same route can then

be used to synthesize these higher lactams, but production costs are higher
than for caprolactam.
New methods have been developed
for caprolactam and are now being used
on a large scale. increasing the price
advantage of caprolactam. Du Ponts
process is based on the nitration of the
saturated cyclohexane ring, followed by
a reduction-dehydration in the presence
of a borophosphoric acid catalyst to
give caprolactam directly (2).
Snia Viscosas process is based on the
reactivity of a tertiary carbon atom on a
6-member ring. Cyclohexane carboxylic
acid, which can be prepared from toluene
( 8 ) , is an example of this type of compound. Reaction with a nitrosation
agent such as nitrosyl sulfuric acid in the
presence of H 2 S 0 4 gives caprolactam
directly with evolution of COa. These
two syntheses comprise fewer steps than
the conventional method and should
accentuate the downward trend of the
caprolactam selling price.
In the case of the amino acids, specific
methods are employed, for no general
synthesis has been found.
For example, the 7-aminoheptanoic acid and
the 9-aminopelargonic acid can be prepared by telomerization of ethylene in
the presence of a halogenated compound
such as CC14 or bromoacetic acid. I n
a first step, a mixture of saturated aliphatic chains is obtained, the 7- and
9-carbon members being prominent
(5). I n a second step, the end groups
are modified into amine and carboxyl
groups to form the w-amino acids.
Amino acids can also be obtained by
using raw agricultural materials, such
as fatty acids. The long aliphatic chain
is split into two parts by oxidation or
pyrolysis, and the amine and acid terminal groups are fixed on one of the
shorter chains, the other remaining as a
by-product. For example, 9-aminopelargonic acid can be synthesized by oxidation of oleic acid, and ll-aminoundecanoic acid may be formed by
pyrolysis of ricinoleic acid, leaving as
by-product the saturated aldehydes,
nonanal and heptanal, respectively ( I ) .

Of dl1 the monomers, amino acids,

or lactams considered to be of commercial interest in large scale manufacture
of nylon, none has reached so far a
production cost as low as caprolactam.
In addition to monomer cost, other factors have to be taken into account in the
final evaluation of the polymer.
Physical Properties

T h e differences in physical properties

between amino acids and lactams are
important in the polymerization process
from a theoretical and technological
point of view.
Amino acids are high-melting point
solids which cannot be purified readily
by distillation. I n some cases, purification is accomplished through the distillation of their methyl or ethyl esters,
which are distillable at high vacuum.
T h e most commonly used method is crystallization from water, in which amino
acids have limited solubility. This solubility decreases as the number of methylene groups in the amino acid becomes
larger, but the solubility increases fast
enough with temperature to permit
easy purification by crystallization in
water. Temperatures above 100' C.
are used to dissolve the amino acid or the
sodium salt of the amino acid, which is
then crystallized by cooling. I n the
final step the monomer is obtained as a
water suspension.
Therefore, the most convenient way
of feeding a nylon monomer into the
polymerization equipment is to use
the water slurry directly at room
temperature or its homogeneous solution at elevated temperature and pressure. I t would be difficult to feed a
monomer melt, since the polymerization
proceeds very rapidly as soon as the
monomer melts (with the evolution of
water).
Lactams, however, are obtained in a
dry state after purification, either by
vacuum distillation for the low members or by crystallization in an organic
solvent for the higher molecular weight
compounds in the series. For example,
caprolactam is distilled and dodecalactam can be purified by crystallization
in cyclohexane. Since lactams are stable
a t their melting points, they are very
easy to handle and can be fed directly
into the polymerization equipment.
T h e polymerization does not start without the introduction of a catalyst and,
therefore, continuous or discontinuous
polymerization processes are very easy
to operate as far as feeding is concerned.
The picture is somewhat reversed,
however, from the standpoint of the
polymerization itself.
Polymerization Kinetics

The polymerization of an amino acid

is a straight-forward dehydration reaction which offers limited possibility of
process modifications.
O n the other

hand, the polymerization of a lactam is a

much more complicated process with
greater versatility.
Characteristics of the polymerization
reaction for the amino acids are:
Yields vary from 86 to 89%, depending on the molecular weight of
t h e amino acids.
T h e r e is no large amount of byproducts, except water.
After polymerization, the polymer
does not need a n y additional treatment.
Characteristics of the polymerization
reaction for lactams are:
T h e yields vary from 95 to 100'%,
depending on the molecular weight of
the lactam.
T h e r e is an equilibrium reaction for
nylon 5 and nylon 6, with substantial
amounts of by-products involved.
Polycondensation of Amino Acids.
T h e polycondensation of amino acids is
a second order exothermic reaction.
No catalyst is necessary to start the reaction, but a sufficiently high temperature
is required. Water is usually removed
at a temperature of about 260" C., and
the reaction is accelerated by applying
vacuum.
I n a discontinuous process, the monomer is fed as a water suspension or as a
solution under pressure. By releasing
the pressure in the polymerization
kettle, this extra water is removed first,
followed by the water coming from the
condensation reaction. The polymer is
extruded in the molten form and processed into pellets.
In a continuous process, the monomer
is fed usually as a water slurry a t room
temperature, but in this case removal of
the large amount of extra water has to
be carried out quickly. In the case of
the polycondensation of the 11-aminoundecanoic acid, a convenient process
which has been in industrial operation
involves spraying this suspension in the
form of very fine droplets on the walls of
a jacketed kettle maintained a t high
temperature. Upon contact with the
heated walls, the water in the droplets is
instantaneously vaporized, and the molten amino acid flows down as polymerization starts.
The problems of rapid heat transfer
are solved in this case because the monomer can drop only when molten or, in
other words, when it has reached a sufficiently high temperature. The molten
low molecular weight polymer can then
be driven continuously into a vertical
polymerization tube. At the bottom of
the tube, polymerization is completed,
and the liquid product may be processed directly.
Theoretical yields would be obtained
except for slight traces of monomer carried over during the removal of water.
By continuous polymerization of nylon
11, for example, yields of 89% are ob-

tained, computed as weight of the dry

polymer to 100% of monomer, compared
with a theoretical yield of about 91%,
which takes into account the loss of one
molecule of water for one molecule of
amino acid.
REACTION
BY-PRODUCTS.The water
formed during the polymerization reaction can come either from an inter- or
an intramolecular reaction-that
is, by
loss of water across 2 molecules of amino
acid or from the same molecule. I n
the case of nylon 7 and nylon 11, the
probability of intramolecular dehydration by forming an 8- or a 12-membered
ring lactam is very remote, but, nevertheiess, this possibility does exist. At
the end of the polymerization reaction,
a very small amount of lactam is formed,
about 1% in the case of nylon 7 and 0.4
to 0.6% for nylon 11,
These lactam by-products are not
extracted from the polymer because
they do not alter the properties of the
nylon, except in some special applications where even very small amounts of
impurities might be objectionable. Once
the lactam is extracted from the polymer, there is no danger of its reformation
during processing of the polymer,
T h e fact that the polymer has reached
its final stage directly at the bottom of the
polymerization tube and requires no
further treatment permits extensipn of the
continuous process all the way to the
end product. I n the case of textile
operations, for example, the molten
polymer can be driven directly into spin
heads and extruded as yarn or staple
fiber continuously.
Polymerization of Lactams. The
mechanism of the polymerization of
lactams has been extensively investigated in the past few years. Several
studies have been published, mainly by
Hermans and his coworkers ( 3 ) . A
catalyst is always needed to start the
reaction. I n this discussion, we are
concerned only with water-catalyzed
reactions.
The mechanism of these reactions
has been well elucidated now. I t is
considered to involve an addition reaction of an open lactam ring into the
growth chain initiated by the combined
catalytic effect of water and acid groups.
Contrary to the amino acid polycondensation, this reaction does not involve
any significant removal of water since
only very small amounts are used as
catalyst. T h e ease of opening the lactam
ring is obviously a function of the number of methylene groups in it. Only
in the case of a 6- or 7-membered ring
is the opening easy. This is an equilibrium reaction.
I n the case of higher lactams, the
water-catalyzed reaction is much more
difficult to accomplish with high degrees of conversion, because of the greater
stability of the large rings. With the
higher lactams, opening the ring is not
VOL. 53, NO. 10

OCTOBER 1961

827

an equilibrium reaction, and once it is

achieved there is very little tendency to
reformation of the lactam. Therefore,
the yield of the reaction approaches
theoretical.
T h e polymerization of dodecalactam
is a good example of this type of reaction.
At the usual polymerization temperature
of 260 C. and polymerization of 30
hours, more than 50% of the lactam is
unreacted. Much higher temperatures
have to be used to carry the polymerization to completion, but a degree of
conversion of almost 100% can be
obtained by processing the lactam at
these high temperatures.
I n the case of the 7-membered dng,
caprolactam, polymerization is easy
to carry out but leads to a n equilibrium
reaction. T h e amount of residual lactam is a function of temperature. At
usual
polymerization
temperatures,
values of about 9 to 10% of residual
monomer are obtained. T h e important work of Zahn and his coworkers (77)
has led to the identification of small
amounts of the linear and cyclic dimers
and trimers in addition to the caprolactam. These low molecular weight substances modify substantially the properties of nylon 6 and usually are objectionable for further processing of the
polymer.
TherTfore, the nylon 6 obtained after
polymerization has to go through additional treatment to remove these
oligomers. T h e usual procedure is a
water extraction, followed by a thorough
drying. If the lactam coming from the
extraction process is fully recovered, a
yield of 95% can be obtained in the
polymerization. This yield reflects the
loss of the unrecovered oligomers and
takes into account the slight resinification occurring during the distillation.
Extensive research has been carried
out on methods for the removal of these
low molecular weight substances. High
vacuum and superheated steam have
proved to be convenient ways of devolatilizing the polymer. T o obtain good
results, the devolatilization has to be
carried out at high temperature, and it
is, therefore, very difficult to obtain
complete extraction because of the
monomer reversion reaction. Only very
fast processes can bring down the amount

of extractables to less than 2%, which

is the maximum limit for further good
processing of the nylon.
These two
processes provide a much easier and
less expensive recovery of the lactam,
compared with its isolation in the water
extraction process.
Concerning the polymerization reaction itself, continuous or discontinuous
processes are easy to carry out so long
as a n unextracted polymer is the final
material desired. This is the case, for
example, in the production of staple
fiber where the unextracted polymer is
spun directly and the extraction process
is applied to the finished product, because of the ease of handling such material.
Nevertheless, complete continuous processes have been set u p with
the vacuum extraction technique, and
the spinning of yarns has been accomplished without any further extraction.
Polymer Characteristics

In the polymerization of amino acids,

the degree of polymerization is controlled
by the use of a small amount of a compound having one kind of functional
group, either basic or acidic. Higher
degrees of polymerization are obtained
by carrying the reaction without any
stabilizer and pushing the reaction as
far as possible by the use of high vacuum.
Nevertheless, the degree of polymerization is never very high.
In the polymerization of lactams,
acid groups are necessary to start the
reaction, and the same compound can
be used simultaneously as a catalyst and
a stabilizer. When high degrees of
polymerization are desired, the stabilizing effect of the acid catalyst should be
avoided. T h e usual procedure is to
catalyze with an amino acid or diacid
diamine salt which has no limiting effect
on the growing of the polymer chain.
With nylon 6 , a very high degree of
polymerization can be obtained conveniently by post polymerization. Following the normal polymerization, this
after-treatment can be applied on the
nylon 6 a t a temperature just below the
melting point. If this nylon has not
been stabilized, a marked increase in
the molecular weight will be obtained
after a few hours.

I
Comparative Properties of Nylon
Nylon
Type

Nylon
Nylon
Nylon
Nylon
Nyion
Nylon

7
8
9
11
12

Me!ting
Poinf,
c.

Specific Gravity,
Gi.ams/Cc.

215
225
195
200
185
180

1 .13
1.10
1 .08
1.06
1 .04
1 .03

Moisture
Regain,

70

4.7
2.4
1 .40
1.2
1.18
1-10
I

828

INDUSTRIAL AND ENGINEERING CHEMISTRY

Comparative Properties

Physical properiies of these various

nylons follow a definite pattern and are
closely related to the number of methylene groups of the polymer chain, as shown
(below). Moisture regain and specific
gravity decrease with a n increasing
number ofmethylene groups. The more
distant the functional amide groups are
in the polymer chain, the closer is the
nylon to a polyolefin.
The mechanical properties in the
plastics and textile applications are
not very different. T h e real differences
in behavior appear mainly when the
properties are measured a t extreme
conditions, such as thoroughly wet
us. dry atmosphere and high compared
with very low temperatures.
The most attractive polyamide is
nylon 7, taking into account the characteristics of the polymerization reaction
and the general properties of the polymer. So far, its cost compared to that
of nylon 6 does not overcome the advantages found in the processing and
its properties. For this reason, so far
no new nylon is produced on a large
industrial scale, other than the four
nylons already mentioned.
Wylon 6,lO and nylon 11, which are
more expensive to make than nylon 6,6
or nylon 6, are produced on a commercial scale because they are sufficiently
different from nylon 6 and nylon 6,6
and have found specific applications.
Bui competition between nylon 6 and
nylon 6,6 might become very acute when
production of the former reaches a large
enough scale. I n this case, too, there
seems to be a definite advantage in the
production cost of nylon 6 comparcd with
nylon 6,6.
literature Cited
(1) Aelion, R., Ann. chim., Puris3, 5 (1948).
( 2 ) England, D. C. (to E. I. du Pont de
Nemours and Co.), U. S. Patent 2,634,269 (Sept. 21, 1951).
(3) Hermans, P. H., Heikens, D., and van
Velden, P. F., J . Poiymer Sci. 30, 81
(19 58).

(4) Klar, R., Hilgetag, G. (to I. G.

Farbenind. A.G.), Ger. Patent 735,727
(April 15, 1943) (addition to Ger. Patent
(5)686,902).
Ncsmejanow, A., Chem. Tech. (Berlin)
I

9. 139 (1957).

(6) Reppe, .W:, Neue Entwicklungen auf

dem Gebiete der Chemie der Acetylens
und Kohlenoxyds, Springer-Verlag,
Berlin, 1949.
(7) Schlack, P. (to E. I. d u Pont de
Nemours and Co.), U. S. Patent 2,283,150 (May 12, 1942).
(8) Snia Viscosa: Belg. Patent 582,793
(Sept. 18, 1 9 5 9 ) .
(9) Wallach, Ann 312, 187 (1900).
(10) Wilke, G., Angem. Chem. 69, 397
(1957).
(11) Zahn, H., Rathgeber, Peter, Rexroth,
E., Krzikalla, R., Lauer, W., Mir6, P.,
Spoor, H., Schmidt, Franz. Seidel, B.,
Hildebrand, D., Zbid., 68, 229 (1956).
RECEIVED
for review November 14, 1960
ACCEPTEDMarch 13, 1961
Division of 138th Meeting, ACS. New
York, September 1960