22

Aromatic Polyamides
LEO VOLLBRACHT
AKZO Fibres and Polymers Research, Arnhem, Netherlands

22.1 WHOLLY AROMATIC HOMOPOLYAMIDES 375

22.1.1 Introduction 375
22.1.2 Meta-coupled Aromatic Polyamides 377
22.1.2.1 Poly(m-phenyleneisophthalamide) Nomex's (Du Pont) and Conexv (Teijin) 377
22.1.3 Para-coupled Aromatic Polyamides 377
22.1.3.1 General 377
22.1.3.2 Poly(p-benzamide) (PBA) 378
22.1.3.3 Poly(p-phenyleneterephthalamide) (PPDT) 378
22.1.4 Future Prospects 382
22.1.5 Attempted Alternative Preparation Methods 382
22.1.5.1 Phosphorylation reaction 382
22.1.5.2 Polymerization from the vapour phase 383
22.1.5.3 Polymerization with thionyl chloride as activating agent 383
22.1.5.4 Polymerization in liquid sulfur trioxide 383
22.1.5.5 Polymerization using silicon tetrachloride 383
22.1.5.6 Polymerization of PPDT using formadinium salts 383
22.1.5.7 Polymerization of p-aminobenzoic acid using carbon disulfide 384
22.1.5.8 Polymerization using phenyl esters of aromatic acids 384
22.1.5.9 High temperature polymerization in the presence of a catalyst 384
22.1.5.10 Polymerization using N-silylated aromatic diamines and aromatic diacid chlorides 384
22.2 AROMATIC COPOLYAMIDES 384
22.3 AROMATIC HYDRAZIDES AND AMIDE-HYDRAZIDES 385
22.4 REFERENCES 385

22.1 WHOLLY AROMATIC HOMOPOLYAMIDES

22.1.1 Introduction
Some 30 years ago, methods were found which permitted the preparation of high molecular
weight fully aromatic polyamides. Special solvent systems were required to obtain high molecular
weights. For these polyamides to be spun into fibres, the existing spinning techniques had to be
adapted to the type of polymer used, but there was no need for the development of new spinning
processes. For example, the para-coupled aromatic polyamides were dissolved in hot 100% sulfuric
acid and the solution thus prepared was spun using the air-gap technique. As a result, the desired
high-strength high-modulus fibres could be obtained in a commercially viable process. The first
commercially produced wholly aromatic polyamide fibre was Nomex'P, introduced in 1961.1 It is a
fully meta-oriented polymer, viz. poly(m-phenyleneisophthalamide). It showed excellent thermal and
flame-resistant properties and, unlike the conventional synthetic fibres, it did not drip. This material
was followed, some years later, by development of the preparation and processing of para-coupled
aromatic polyamides (Section 22.1.3).
Both the meta and para polymers have become of great commercial importance. Since the wholly
aromatic polyamides show a tendency to decompose during or even before melting, they must be
spun from solution. The meta product [Nomexw (Du Pont) and Conexw (Teijin)] is used in cases

375
376 Synthesis by Step Polymerization

where flame resistance and thermal stability are required. The para products [Kevlarw (Du Pont)
and Twaronw (Akzo)] are not only flame resistant and thermally stable, but also display exceptional
strength and modulus values. Because of the special fibre properties which are unique and unknown
for commercially available synthetic and chemical fibres, these products form a class apart, denoted
by the generic standard name of aramides.? Reviews which in part or entirely cover the subject of
aromatic polyamides have been published in the literature. 2 - 8
There are a large number of wholly aromatic polyamides if all the possible ortho-, meta- and para-
oriented monomers are combined. However, only two of them are of commercial importance:
poly(m-phenyleneisophthalamide) (1; Nomex'") and poly(p-phenyleneterephthalamide) (2; PPDT,
Kelvare, Twaronw), PPDT is a combination of the abbreviations used for the monomers,
p-phenylenediamine (PPD) and terephthalic acid (T). Initially, Du Pont used poly(p-benzamide)
(PBA), but later on they changed over to PPDT. 2

-(-NH-o-NH~-cnt JNH-Q-'NHC
\ -
r \ r-t
II~-II" o 0
(1) (2)

The wholly aromatic polyamides cannot be prepared by melt polycondensation. The potential
polyamides either do not melt or melt at high temperatures with decomposition. Many aromatic
diacids will decarboxylate? and the aromatic diamines are readily oxidized and have a tendency to
sublime.P: 10 Consequently, use is made of low temperature polymerization methods. Since the
reactivity of aromatic diamines and aromatic dicarboxylic acids is too low, it is generally necessary
to employ aromatic carboxylic acid chlorides (equation 1). An acid acceptor is needed to bind the
hydrochloric acid evolved. Usually, the polymerization proceeds very rapidly. Two methods are in
use, viz. the interfacial polymerization method (a two-phase process) and the solution polymeriz-
ation method (a single-phase process). In interfacial polymerization, the reaction takes place at the
interface between a solution of the diacid chloride in an organic solvent (immiscible with water
under the conditions applied) and an aqueous solution of the diamine. 1 1 In the solution polymeriz-
ation method, the reaction simply takes place in a homogeneous solution. For the solution
polymerization of aromatic polyamides, it is advantageous to use aprotic polar amide solvents, such
as dimethylacetamide (DMAc), N-methylpyrrolidone (NMP) and hexamethylphosphoramide
[HMPA; phosphoric tris(dimethylamide)]. Dimethylformamide (DMF) is unsuitable because it
reacts with acid chlorides, nor is dimethyl sulfoxide (DMSO) of any use because of its violent
reaction with acid chlorides. HMPA, a powerful solvent, must not be used, since it is a carcinogen in
rats.P The dissolving power of the amide solvents can be increased by addition of salts, such as
lithium chloride or calcium chloride. The amide solvents further serve as acid acceptors, which is
why such compounds do not need to be added. Though these solvents are far weaker bases than the
primary aromatic diamines, the huge excess of solvent brings the polymerization to completion
without loss of diamine as an inactive hydrochloride. A further advantage of the amide solvents may
appear in the case of the more soluble aromatic polyamides, such as Nomexw. When the hydro-
chloric acid formed in the polymerization is neutralized with calcium hydroxide, calcium chloride, a
solvating agent, is formed, which leads to dissolution of the polymer so that the reaction mass can be
spun directly (combined process).

o 0
II II
ArNH 2 + Ar/CCI ----+ ArNHCAr' + HCI (1)

Suggestions for Nomexw manufacture are given in refs. 2 and 7. Proposals for a mechanism
accounting for the role of lithium chloride as a solvating agent for aromatic polyamides in DMAc
can be found in refs. 13 and 14. In general, high molecular weight wholly aromatic polyamides can
be obtained more consistently by low temperature solution polycondensation than by the interfacial
method.' The polymer prepared is usually isolated by coagulation and neutralization with aqueous
alkali, filtration, washing with water or an organic solvent and drying. The dry polymer is very liable
to be electrostatically charged. The two aromatic polyamides which are of commercial interest
(1 and 2) will now be discussed separately. A section will also be devoted to PBA, the forerunner of
PPDT. The same procedures can be followed for other aromatic polyamides and copolyamides.
The aromatic copolyamides are usually easier to prepare because of their better solubility. They will
be discussed in Section 22.1.4.
 Aromatic Polyamides 377

22.1.2 Meta-coupled Aromatic Polyamides

22.1.2.1 Poly(m-phenyleneisophthalamide) Nomexs (Du Pont) and Conexv (Teiiin)?
This polymer is prepared from m-phenylenediamine and isophthaloyl dichloride (equation 2). It
can be prepared by interfacial polymerization or by solution polymerization. Examples of the
interfacial method can be found in refs. 15 and 16, and of solution polymerization in refs. 4 and 16.
Products of sufficiently high molecular weight are formed.

o
~
~ ----. 1\NH-o-INH~--fjrfi
nC\goICC\
~ 6~O"
t + 2nHC\ (2)
Nomexw is used when heat and flame resistance are essential. Because of its attractive electrical
properties, which are retained at high temperatures, Nomexw is also used as an electrical insulating
material, in the form of fibre or paper.

22.1.3 Para-coupled Aromatic Polyamides

22.1.3.1 General
The para orientation leads to less solubility, generally. For this reason, only a few solvent systems
have been found that are capable of producing polyamides with a molecular weight sufficiently high
for spinning purposes. If interfacial polymerization is used to produce these rigid-rod extended-
chain polymers, it results only in low molecular weights.l": 18
The view that para-coupled aromatic polyamides, because of their rigid chains, will give materials
with exceptional properties, such as high melting points, thermal stability and high strength and
modulus, dates back to the 1960s. (See, for example, a review by Mark on polymer applications,
published in 196519). In 1961, the PPDT polymer itself was mentioned and exemplified in a Du Pont
aramid patent.!" The solvent HMPA was used and an inherent viscosity of 1.9dl g-1 was attained.
In a subsequent patent.i? dealing with the heat treatment of aramids, the PPDT polymer is also
mentioned specifically. A publication by Preston and Smith in 1966 revealed an initial modulus of
245 g denier- 1 (denier = weight in g of 9000 m of fibre) for an all-para-ordered aromatic co-
polymer.i! The spinning of various poly(terephthalamide)s, dissolved in high concentrations in
sulfuric acid, is described in a Celanese patent published in 1965.2 2 The use of air-gap spinning in the
case of wholly aromatic polyamides, in order to improve the spinning process and the fibre
properties, was disclosed in a Monsanto patent of 1968.2 3 High polymer concentrations of 10-30%
were employed. Finally, they were used commercially by Du Pont in 1970. The first all-para
homopolymer to be used was PBA, which was replaced later on by PPDT. 24,34 Akzo started pilot-
plant production of aramid fibres in 1977.
The polymerization of para-coupled polymers is sometimes associated with the peculiar phe-
nomenon of liquid crystallinity, also called mesomorphism or solution anisotropy. We shall discuss
this briefly.
The all-para coupling causes the polymer units to be linked so as to extend the chain in the same
direction, while the amide bonds are presumed to be predominantly in the trans configuration. These
rigid extended-chain polyamides, which have a rod-like shape, lead to mesomorphic (liquid
crystalline, anisotropic) solutions beyond a certain concentration. This was predicted by Flory in
19562 5 and proved experimentally by Hermans in 1962.2 6 As the concentration of rod-like molecules
is increased, the system may simply become a saturated solution with excess polymer or, to
accommodate more dissolved polymer in a particular space, is forced to form regions or arrays in
which the polymer chains are arranged in parallel. Continued addition of polymer now enlarges the
regions' of the ordered state, which for aromatic polyamides is the nematic phase. A schematic
representation of polymer states in solution, including that of random coils, is given in Figure 1.4 , 2 6
Some polyamides with stiff chains in the extended state which have been shown to yield liquid-
crystalline solutions are given in Table 1.4 Note that a fully aromatic system is not 'required per see
The occurrence of a liquid-crystalline phase is revealed by some special phenomena, such as
opalescence upon stirring and variation in solution viscosity. Upon increasing the polymer concen-
tration in the isotropic region, the viscosity first exhibits a normal increase (see Figure 24 ) up to a
critical point where an anisotropic liquid-crystalline phase is formed, after which the solution
viscosity decreases with increasing polymer concentration. Beyond a certain point, the viscosity
increases again. This viscosity behaviour of the anisotropic solution has been demonstrated by
378 Synthesis by Step Polymerization

Hermans'" for a different polymer, viz. poly(y-benzyl-L-glutamate). For spinning purposes, PPDT in
a high concentration is dissolved in 100% sulfuric acid, which gives rise to anisotropy of the solution.
The effect of the anisotropy of spinning solutions on yarn properties is smaller than generally
assumed. Weyland"? has elaborated some hypotheses on this subject.

Figure 1 Schematic representation of polymer states in solution: (a) random coils; (b) random rods; (c) rods in liquid-
crystalline arrays; and (d) nematic state for one array (reproduced with permission from ref. 4)

At a certain molecular weight, the rod-like character of the all-para polyamides cause the inherent
viscosity 1Jinh to be higher than for the corresponding meta polymers. According to ref. 28, an 1Jinh
value of 0.4 dl g-l for poly(m-benzamide) approximately corresponds to an 1Jinh value of 1.7dl g-l
for poly(p-benzamide). Furthermore, it makes a difference whether the inherent viscosity is deter-
mined in amide solvents containing lithium chloride or in concentrated sulfuric acid. The con-
siderable difference observed is attributed to the formation of aggregates in the amide solvent. 28,29
In ref. 29, molecular weight data as functions of the inherent viscosity are given for PBA and
PPDT. For spinning purposes, the inherent viscosity of the all-para-coupled aromatic polyamides is
reported to have a value of 5dlg- 1 or higher.P"

22.1..3.2 P'oly(p-benzamide) (PBA)

A comprehensive review of the synthesis of this polymer has been given by Kwolek and co-
workers.i ' The monomer (3) must be prepared separately (Scheme 1). Note that the amino group is
masked as the hydrochloric acid salt in order to prevent spontaneous polymerization. Even so, the
hydrochloric acid salt of p-aminobenzoyl chloride is unstable, as it is sensitive to moisture, light and
heat. A brief summary of the special problems encountered in using this type of AB monomer for
polymerization is given by Morgan.F To start the polymerization, the salt is dissolved in one of the
aprotic polar amide solvents mentioned previously, thereby releasing the amine group from the
hydrochloride, so that the polymerization can proceed. The polymer is isolated as described before.
Another possibility is to transform the reaction mixture into a spinning dope by the addition of
lithium hydroxide, thus producing the solvating agent lithium chloride in situ (see introduction). The
liquid anisotropic dope can be dry spun or wet spun. 3 1 , 3 3
Despite the disadvantages of using monomers such as (3), Du Pont started with PBA as a fibre
material (first generation Fibre B), probably with a view to using a combined polymerization-spin-
ning process. However, a smooth particle-free spinning solution of high molecular weight PBA is
difficult to prepare by a combined polymerization-spinning process and will certainly be attended
by spinning problems. Later on, Du Pont switched over to the use of PPDT as a fibre starting
material, which does not permit the use of a combined process.P" The fibres (second generation Fibre
B), which are air-gap spun from sulfuric acid, have a considerably higher strength than those ofPBA.

22.1.3.3 Poly(p-phenyleneterephthalamide) (PPDT)

This polymer is prepared from two monomers in a typical AA-BB polymerization, viz.
p-phenylenediamine (PPD) and terephthaloyl dichloride (TDC) (equation 3). PPD is dissolved in the
 Table 1 Some Polyamides Yielding Liquid-crystalline Solutions"

o o
-NH-oJ- -NH-Q--OJ!- -NH-Q-'NHC-Q-'
o
!!- - 11-

o
-NH-Q-NH~-O-O-!!-
o
-NH-Q-NHfi-Cl 0 -NH-Q-'NHC-D--!!N
'\ ~
- II -
o -
~
-NH

-NH~NHfi~ 0 -NH-o-'NHC~~ ~
~

~NHc~{I
II
o -
'\ rl.
-
- g ~-C-
3
~
~
~.

~
o~
Q

~
3

0
CI ~
~

- N-Q-
NHC~
g~_ -NH-o-NH~-o-N\--oJ_
~

H_

-NH
NHC~'
1\
o -
~ - -NH-o-N\-o-NH~-o-N~-oJ_
o

• Reproduced with permission from ref.4.

W
-J
\C
380 Synthesis by Step Polymerization

30

20
I sotropic ___ Optically
o - anisotropic
CL

10

4 5 6 7 8 9 10
Weight percent polymer in solvent

Figure 2 Effect of polymer concentration and the formation of a liquid-crystalline solution on the bulk viscosity of solutions
ofpoly(chloro-l,4-phenylene/l,4-phenylene-2,6-naphthalamide) (70/30)in hexamethylphosphoramide-N-methylpyrrolidone
(1-1, vIv) containing 2.9% LiCI at 27°C; polymer '7inb = 2.0. Bulk viscosity was determined with a Brookfield Model RV
viscometer with a no. 6 spindle at 10 r.p.m. (reproduced with permission from ref. 4)

Intermediates
0
2S0CI 2 ~
OSNOCI + S02 + 3HCI

0
3HCI
ether
~ HCI'H2NOCI + SOCl 2

Polymerization

amide. ~
solvent
+ 2 amide·HCI

or

+
amide ~
solvent + S02 + amide·HCI

Scheme 1 Poly(p-benzamide) preparation (reproduced with permission from ref. 31)

amide solvent and TDC is added with cooling in the molten state or as a solid material (powder or
flakes). The polymerization is very fast. The kinetics in HMPA have been studied by Borkent and
co-workers." by applying stopped-flow soectrophotometry.

nCI~OCI
o 0
amide .~
solvent
-t N H- o -NHC
r "
-
-r\-r-t
~\JIf-~ n

+ 20 amide·HCI (3)
 Aromatic Polyamides 381

In a Celanese patent, the premixing of the solid reactants PPD and TDC is described.l" Care
should be taken that the solid reactants do not contain water, oxygen or carbon dioxide. This
method does not seem to offer special advantages, however.
PPDT is even less soluble than PBA. 3 7 So far, only two solvent systems have been found suitable
for solution polymerization on an industrial scale in which polymer of a sufficiently high molecular
weight is obtained. These systems are a solvent mixture of HMPA and NMP in the volume ratio 2: 1
and an NMP-ealcium chloride mixture. The use of a mixture of HMPA and NMP leads to higher
molecular weight polymers than the use of the neat solvents separately. 38,39 However, in a
continuous process, using a special technique of premixing the reactants and extrusion, use is made
of neat HMPA. 4 0 - 4 2 TheHMPA system was used by Du Pont until 1982. The NMP/CaCI 2 system
was discovered and patented by Akzo.t" As HMPA was found to be a carcinogen in rats,'? the
NMP/CaCI 2 system has become of special importance, especially since, after many years, no
commercial alternative has yet been found. As HMPA is no longer permitted for use in commercial
operations, we shall discuss briefly the use of the NMP/CaCI 2 system. Before it became known that
HMPA was a carcinogen in rats, Akzo had already found the NMP/CaCI 2 system as a result of a
special study to find an alternative to HMPA. The study was started because the use ofHMPA on a
plant scale would present serious difficulties. The compound is thermally and chemically unstable,
especially under acidic conditions, which results in incomplete recovery. Another objectionable
aspect is the formation (during polymerization, coagulation and recovery) of phosphorus-containing
degradation products. At the time (1974) the prospects of finding an alternative were not great.
World-wide, the prevailing idea was that amide solvent/salt systems were inferior to the mixed
solvent system HMPA/NMP"a conclusion which had been clearly expressed by Fedorov et al., who
had tried in vain to find an alternative.P" Sokolov had the same view.t" Of the unattractive amide
solvent/salt systems, DMAc/LiCI was considered to be the best. 14 , 3 8 , 4 4 Of the many possible
combinations, the NMP/CaCI 2 system was not considered by anybody; apparently 14, 38,44 because
it was expected to be even less attractive than the DMAc/LiCI system. Yet, it turned out that in this
system the same results can be achieved as in HMPA/NMP, but, to that end, it is necessary to use a
large amount of calcium chloride, preferably surpassing the solubility limit of 6% for calcium
chloride in NMP at room temperature. This seems strange and illogical, simply because of the
apparent uselessness of non-dissolved calcium chloride particles. However, when the polymerization
is started by the introduction of terephthaloyl dichloride, the calcium chloride particles quickly
dissolve, probably due to the complexation of calcium chloride with the amide groups which have
just formed, as a result of which calcium chloride is removed from the solution, which in turn results
in dissolution of the non-dissolved particles. Therefore, the amount of calcium chloride present
should be larger than the amount which dissolves at room temperature. The excess of calcium
chloride may then be present in a solid or supersaturated state. In our opinion, the complexation
renders the PPDT polymer more soluble, keeping it in a swollen state when a high degree of
polymerization is reached, as in the case ofHMPA/NMP. In this swollen state, the polymerization is
apt to continue, because it is still accessible to reactive species. Finally, a polymer is obtained that is
no different from the polymer produced in HMPA/NMP. The amount of calcium chloride is related
to the amount of polymer. For satisfactory results, the weight of calcium chloride should not be
lower than the weight of polymer to be formed (i.e. approximately equimolar), but preferably higher.
The polymer concentration should be as high as possible, of course, but the concentration to be
obtained depends on the equipment used and should be determined experimentally. The same
applies to the amount of calcium chloride. Amazingly, the shape of the apparatus and the mixing
efficiency can have a tremendous effect on the inherent viscosity. This is illustrated by the data in
Table 2. In this connection, a role is also played by the high speed of the polymerization reaction and
the resulting rapid onset of gelation.
Table 2 Influence of Apparatus on rJinh a

Apparatus

Drais kneader 1t Ib 0.7

Glass flask with anchor stirrer 2.3
Waring Blendor II 3.8
160 I Drais TSc 5.2

a Conditions: polymer concentration 80/0, CaCl 2 12% (both calcu-

lated on 100 parts by weight of NMP); initial temperature 0-20°C.
b Planetary mixer from Drais Ltd., Mannheim, West Germany. C Tur-
bulent Schnellmischer.
382 Synthesis by Step Polymerization

The polymerization is carried out with cooling and exclusion of moisture. Under proper
conditions, the viscosity is fairly independent of the monomer (polymer) concentration applied. For
HMPA/NMP, this dependency has been reported.t"
The effect of the calcium chloride concentration in NMP on the inherent viscosity of the polymer
produced differs strongly from that of lithium chloride in, for example, DMAc. At a low lithium
chloride concentration in DMAc, a peak is found in the curves of the inherent viscosity as a function
of lithium chloride concentration.l" Up to higher lithium chloride concentrations, the inherent
viscosity remains at a constantly low level. In contrast, after an initial steep rise, the inherent
viscosity of the polyamide in the NMP/CaCI 2 system will continue to increase with the calcium
chloride concentration and will remain far above the peak viscosity in the DMAc/LiCI system. The
absence of a peak viscosity is of importance in commercial production, because it makes the process
less sensitive to slight variations in the salt concentration. At a certain stage, depending on the
equipment used, the calcium chloride content has risen to the extent that it prevents proper mixing.
The inherent viscosity will then level off and begin to decrease. The function of calcium chloride in
PPDT polymerization in NMP is unique. An important point is the recovery of NMP and calcium
chloride, which proceeds without any problem.
Northolt''P-?" has determined the crystal and molecular structure of PPDT by X-ray diffraction.
Further studies by the same author on the elastic properties and the stress-strain behaviour in
relation to structure can be found in the literature.t" - 51
Kevlarw and Twaronv are used when properties such as high strength, high modulus and low
density are of advantage, viz. ropes, cables, reinforcement of rubber (tyres) and plastics. 52,53 An
interesting application may be the replacement of asbestos in automotive brake linings.

22.1.4 Future Prospects

It seems most probable that Nomexw will maintain its established position. No major changes can
be foreseen in its synthesis and spinning.
In the field of para-coupled polyamides, PBA seems to have hardly any future. The complicated
monomer synthesis needs to be simplified and the yarn properties improved. This is not the case for
PPDT, the polymer on which Kevlarw and Twaronw are based. Its future is promising. The
monomer synthesis is attractive, the polymerization may be performed very well in the almost
harmless and easily recoverable NMP/CaCI 2 system and the spinning from 100 % sulfuric acid using
the air-gap technique offers no basic problems. Improvement of the already exceptional yarn
properties are to be expected as a result of further optimization of the process.

22.1.5 Attempted Alternative Preparation Methods

Several investigations into finding different ways of preparing PPDT and PBA have been made by
various authors. They are described below.

22.1.5.1 Phosphorylation reaction

This method involves the direct polycondensation of aromatic amino acids, or of aromatic
diamines and aromatic diacids, in the presence of an aryl phosphite and an organic base. It has been
the subject of several publications. In 1974,54Yamazaki, Higashi and Kawabata published an article
on a procedure for the synthesis of, inter alia, aromatic polyamides using dicarboxylic acids and
diamines in the presence of triphenyl phosphite in NMP with pyridine as base. A feature of this
method is that the use of acid chlorides is avoided. Low molecular weight products were obtained. In
1975, Yamazaki, Matsumoto and Higashi improved the process, predominantly for PBA, by the
addition of lithium chloride.V The molecular weights obtained were still too low. Over the years, the
process was further improved. In 1978, Preston and Hofferbert stressed the importance of tem-
perature control." In 1982, Higashi, Ogata and Aoki managed to increase the inherent viscosity of
PPDT to 4.5dlg- 1 by adding calcium chloride to the NMP/pyridine/LiCI medium.i" Finally, in
1984,57,58 Krigbaum, Kotek, Mihara and Preston arrived at an inherent viscosity of 6.2 dl g-1 for
PPDT by increasing the reaction temperature from 100°C to 115 °C. Strangely enough, these
improvements do not apply to PBA; since 1975 the maximum inherent viscosity has remained on the
1.8 dl g-1 level. These results show that unexpected differences may be encountered in the prep-
 Aromatic Polyamides 383

aration of two very similar polymers. Though for PPDT an inherent viscosity of 6.2 dl g - 1 has been
obtained, a rather complex reaction medium is required. Furthermore, the concentration of
reactants is low."? 0.08 moll- 1, vs. a value of 0.25 moll- 1 for the HMPAjNMP systerrr'" and
~ 0.25 mol kg - 1 for the NMPjCaCl 2 system. Application on an industrial scale is not expected for
the time being.

22.1.5.2 Polymerization from the vapour phase

Demonstrating a skillful experimentation technique, Shin,"? and Ikeda and co-workers'P:"! were
able to react PPD and TDC in the vapour phase in a temperature range of 200-300 °C. After its
formation, the polymer deposited on specially provided foils and films. While the inherent viscosites
usually ranged from 2 to 3.6 dl g - 1,61 a maximum value of 5.3 dl g - 1 was obtained. 59 However, this
high value is only obtained in a small proportion of the polymer produced, widely different values
being found at the various sampling spots. Most of the polymer has an inherent viscosity ~ 3 dl g - 1.

22.1.5.3 Polymerization with thionyl chloride as activating agent

The direct synthesis of wholly aromatic polyamides using thionyl chloride as an activating agent
has been reported,62-64 with NMP as the preferred solvent.P? The monomers used included PPD
and terephthalic acid.?" The inherent viscosities are low. For PPDT, an '1inh value of 0.67 dl g-l is
mentioned.t" For the reaction of p-aminobenzoic acid with thionyl chloride, see Scheme 1.

22.1.5.4 Polymerization in liquid sulfur trioxide

It has been found possible to apply the direct condensation of terephthalic acid and PPD sulfate
in sulfur trioxide/" - 67 A major side-reaction is the sulfonation of the aromatic ring. Solution
anisotropy was found to take place in the reaction mass. The reaction mass could be spun, but the
process was impeded by the tremendous evolution of heat during coagulation of the yarn in water as
well as by the weakness of the gelatinous fibres produced. The latter phenomenon has been
attributed to the hydrophilicity brought about by the introduction of the sulfonic acid group. The
intrinsic viscosities were low (~2.2 dl g - 1). The synthesis of sulfonated PPDT has also been
performed by reacting 1,4-bis(trichloromethyl)benzene and PPD sulfate in sulfur trioxide.P" A low
viscosity polymer resulted ('1inh ~ 1.2 dl g-I).

22.1.5.5 Polymerization using silicon tetrachloride

p-Aminobenzoic acid has been polymerized to PBA, and p-phenylenediamine with terephthalic
acid to PPDT, in the presence of silicon tetrachloride as a condensation agent.?" The reaction was
carried out under reflux in pyridine or a mixture of pyridine and chlorobenzene. For PBA, an
intrinsic viscosity of 1.4dl g - 1 was found, for PPDT a value of 0.6 dl g - 1.

22.1.5.6 Polymerization of PPDT by using formamidinium salts

In this process, p-phenylenediamine is converted first into N,N-p-phenylenebis(N',N'-dimethyl-
formamidine), which forms a salt with terephthalic acid after its addition. Upon heating this salt
to above 225°C, PPDT is formed with evolution of dimethylformamide (DMF; equation 4). The
intrinsic viscosity is low, ~ 0.94 dl g - 1.70

-----I~~ 1:1 salt

o
II
2nHCNMe 2 (4)
384 Synthesis by Step Polymerization

22.1.5.7 Polymerization ofp-aminobenzoic acid by using carbon disulfide

p-Aminobenzoic acid can be reacted with carbon disulfide to give an isothiocyanate which
condenses spontaneously to an oligomeric product. Upon heating the oligomer, carbon oxysulfide is
released with formation of PBA (equation 5).71 The conversion is low, 340/0. A maximum inherent
viscosity of 4.8 dl g-1 has been reported."!

(5)

22.1.5.8 Polymerization using phenyl esters of aromatic acids

Heating phenyl p-aminobenzoate to 325°C produces oligomeric PBA with evolution of phenol,
which is removed by distillation. The solid mass is subsequently heated to 425°C (solid-state
polymerization). PBA with an inherent viscosity of 1.9dl g-1 is formed.F The same procedure is
followed to obtain PPDT by reacting PPD with diphenyl terephthalate. The polymer has an
inherent viscosity of 2.5 dl g-1. 73

22.1.5.9 High temperature polymerization in the presence of a catalyst

PPD and terephthalic acid are heated in a mixture of diphenyl sulfone and p-xylene in an inert
atrnosphere.?" The catalyst consists of a mixture of p-toluenesulfonic acid and boric acid. The
temperature is gradually increased to 375°C. p-Xylene and water are distilled off. An inherent
viscosity of 2.09 dl g - 1 is obtained.

22.1.5.10 Polymerization using N -silylated aromatic diamines and aromatic diacid chlorides
This recently reported." reaction proceeds as shown in equation (6). Silylated m- and
p-phenylenediamine have been used; they were prepared by reaction of the diamines with trimethyl-
silyl chloride in the presence of triethylamine. The polymerization took place at -10°C in the
system HMPA/NMP containing approximately 50/0 of lithium chloride. High inherent viscosities
were obtained, also in the case of PPDT, for which a value of 7.4 dl g-1 was found. It is clear,
however, that this reaction is only useful in the laboratory.

o0 0 °
nMe 3SiNHArNHSiMe 3 II "
+ nCICAr'CCI ------+ 2nMe 3SiCI II "
+ +NHArNHCAr'C+ (6)
n

22.2 AROMATIC COPOLYAMIDES

By following the same procedures that apply to the manufacture of aromatic homopolymers.t'
viz. amine/acid chloride reaction in a solution ofNMP/CaCI 2 (or weaker solvent systems in the case
of easily soluble polymers), one can, of course, prepare copolymers (equation 7). Various systems
have been proposed for solution polycondensation of the amine/carboxylic acid system using
condensing agents. Typically, such schemes (notably triphenyl phosphite/pyridine P- 76) are more
effective for aromatic polyesters than for polyamides, and, among the polyamides, are more useful
for the more soluble polymers than for the poorly soluble products (equation 8). By carrying out the
reaction at high temperature, however, acceptable molecular weights can be attained.": 57
solvent
ArCOCI + Ar'NH 2 -----+~ ArCONHAr' + HCI (7)

ArC0 2H + Ar'NH 2 solvent

--..~ ArCONHAr' + PhOH + (PhOhPOH (8)
(PhOhP. pyridine
 Aromatic Polyamides 385

A third route 77 is applicable to copolyamides where the molten state is accessible, viz. acidolysis
(equation 9). This reaction type has been studied intensely in connection with all-aromatic poly-
esters;" but aromatic poly(ester amide)s can be made along the same lines.??

i
heat
ArC0 2H + Ar'NHAc ------+J ArCONHAr' + AcOH (9)

22.3 AROMATIC HYDRAZIDES AND AMIDE-HYDRAZIDES

Condensation of diacid chlorides with hydrazine or with preformed bishydrazides can be
performed in solution (DMAc, NMP with salts if needed). Copolymers will stay in solution: the
solution can be spun as such. Most attention in this field has centred on the semi-regular
copoly(amide-hydrazide) from 4-aminobenzhydrazide and terephthaloyl chloride. Attractive yarns
have been obtained after hot drawing. 3,80 Intense dehydration of hydrazides, either by heating after
isolation'" or in solution in a dehydrating agent, such as polyphosphoric acid or oleum, produces
poly(oxadiazole)s.82,83

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