Review

Polyamides – Still Strong After Seventy Years

Dedicated to the memory of Kalev Pugi, 1925–1984, innovator and inventor in the manufacture of
polyamides and polyamide monomers, friend and inspiring leader to many of us in the DuPont
Company

Keith Marchildon

Polyamides are a subject of enduring interest because of their variety, their complex internal
structures, their commercial importance and versatility, and their various chemistries of
preparation and of long-term use. The present review introduces these polymers and then
discusses the first of the above aspects, namely the variety of the poly-
amides. Here, together, the full family is presented, classified con-
veniently according to the types and combinations of monomers from C
+
which they are constructed. N H
- O C
Introduction C
This introduction presents information about definitions,
origins, and structure of the polyamides. It then explains
the eight classifications that have been chosen for the
present survey. Definitions
Polyamides have been with us since the 1930s – the dawn
of the synthetic polymer age. The development of poly- A polyamide is a polymeric substance, generally linear,
amide technology established many of the principles and with recurring amide groups as an integral part of the
practices for polymerization in general, laying the ground- polymeric chain. Since the nitrogen atom bears only one
work for the great array of materials that have followed. hydrogen atom, these amides are of secondary type. The
Polyamides continue to enjoy a respected place among group is illustrated in Formula 1, along with other
polymeric materials and, although they have been sup- structures that form the linkages in other polymers.
planted in some applications by newer better-suited Polyamides, and the other polymers based on the
formulations, they remain important in both volume and linkages of Formula 1, are among the class of polymers
in their ability to meet specific needs. In fact some of the generally formed by the mechanism of ‘‘step-growth,’’ in
competition has been internal, in that newer types of which reaction takes place between multifunctional
polyamides with superior properties have sometimes (usually difunctional) molecules, where each new bond is
edged out (but more often augmented) the old originals. created as a separate step, neither depending on or causing
Of the polyamides, it may be said that nature and the any other step. Polyamides are formed from low-molecular-
chemists have given a gift of great practical utility to weight starting materials (monomers), forming molecules
humanity. In terms of engineering, the polyamides embody of increasing length which react with each other and with
reaction engineering in its most general sense where a residual monomers until a material of useful average
combination of chemical and physical transformations is molecular size is achieved. In some cases (e.g., nylon 6 or
engineered to make useful products. PA 6) there is a ‘‘chain-growth’’ polymerization path where
monomer (caprolactam) is continually added to the
K. Marchildon growing chain, but the reversibility and relative slowness
842 Nordic Avenue, Kingston, Ontario K7M 4T1, Canada of this mechanism distinguishes it from the chain growth of
E-mail: keith.marchildon@sympatico.ca vinyl polymers.

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22 ß 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim wileyonlinelibrary.com DOI: 10.1002/mren.201000017
Polyamides – Still Strong After Seventy Years
O O
C C C C
N ing from McGill University, Montreal. He worked
O N O
H a C H c
C C
O b C
O expansions, mathematical models and company-
C C
C C C
N N H f
O N O
H H
d C C
C technical rank of DuPont Fellow. He participates
e C
Formula 1. Common polymer linkages (a: amide, b: ester,
c: urethane, d: urea, e: imide, f: ether).
The monomers of the earliest polyamides were straight-
chain, aliphatic, and difunctional. Subsequently monomers
have been introduced containing aliphatic rings, aromatic
rings, and additional functionality; also, in some cases, the
monomers are joined with non-amidic monomers.
Some common terms used with polyamides are

Nylon, defined by the US Federal Trade Commission[1] as
any polyamide having less than 85% of the amide
groups directly connected to two aromatic groups. This
definition is specifically for a fiber but is conveniently
extended.

Aramid, a polyamide having 85% or more of the amide
groups directly connected to two aromatic groups.

Polyphthalamide (PPA), defined by the American Society
for Testing Materials[2] (ASTM) as a polyamide in which
the residues of terephthalic acid (TPA) or isophthalic acid
(IPA) or a combination of the two comprise at least
55 mol-% of the dicarboxylic acid portion of the
repeating units in the polymer chain. PPAs are
considered as nylons.
Along with its essential role in joining small molecules
into large ones, the amide group, because of its polar nature,
dictates most of the character of the polymer. Amide groups
participate in hydrogen bonding to one another, which
restricts inter-chain mobility, resulting in strength and in
strength retention as temperature increases. In most poly-
amides, hydrogen bonding pulls many of the chains into
ordered crystalline regions, which further augment the
strength and melting point of the polymer. Hydrogen bond-
ing also takes place between polymer and water and other
polar absorbed substances. If in the crystalline region the
amides happen to align in the same direction, the polymer
displays notable behavior under electrical stimuli.[3,4] Aug-
menting the effect of the amide dipole, the more recent
incorporation of aromatic monomers, particularly where
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www.mre-journal.de
Keith Marchildon is a professional engineer with
Bachelor’s degree and PhD in chemical engineer-
C
for DuPont (and more recently for Invista) from
1964 to 2008. His principal field was the poly-
merization of nylon, with inventions, low-cost
O wide training courses, all based on his funda-
mental studies of the processes and chemistry.
For this and other work he was awarded Dupont’s
Pedersen Medal and was promoted to the highest
in the teaching of Process Design and of
Mathematical Modeling at Queen’s University
in Kingston, Ontario, Canada. He resides in
Kingston with his wife Joan.
conjugation occurs between the benzene double bonds and
the acyl double bond of the amide link, adds further to the
strength and temperature-resistance of the polymer.
Good starting points for a broad general view of the
polyamides are the articles by Weber[5] and Zimmerman.[6]
Other, more expansive, references are the handbooks edited
by Kohan[7] and by Becker et al.[8]
Beginnings
The two original polyamides, nylon 66 and nylon 6, were
invented in the 1930s, but their origins were in the 1920s
when Herman Staudinger developed the concept of natural
polymers as large molecules comprising repeating small
units or segments.[9,10] On this basis, Wallace Carothers,
working for DuPont, reasoned that synthetic polymers
could be made by the chemical joining of small molecules,
and he eventually settled on diamines and diacids as the
molecules of choice, reacting them with each other to
produce amide linkages and large molecules consisting of
100 and more repeat units. The reaction is shown in
Scheme 1.
Many combinations of diacid and diamine were tested
and the choice was finally made of the two six-carbon
starting materials hexamethylenediamine (HMD) and
adipic acid, as shown in Formula 2. Contributing to this
decision were at least three factors:

The high melting point (255–265 8C) and good strength
of the polymer.
O
O
NH + C + H2O
H C N
HO H
Scheme 1. Direct formation of amide linkage.
Macromol. React. Eng. 2011, 5, 22–54
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O O
HN H
NH HO OH
H +
O NH
Formula 2. Hexamethylenediamine (HMD) and adipic acid.

The low, manageable co-production of cyclic products.

The potentially relatively low cost of raw materials
because their six-carbon content allows them to be
produced from benzene.
The material was first made on February 28, 1935, and a
patent[11] was awarded on February 16, 1937. The first
commercial plant for fiber from this first polyamide – called
nylon 66 (or, more generically, PA 66) because of the six
carbons in the diamine and diacid, respectively – started up
in Seaford Delaware in December 1939. Concurrently
DuPont was also manufacturing nylon 66 in the form of
bristles and monofilaments (e.g., fishing line) and as a
molding resin. Two accounts of the invention and commer-
cialization of nylon 66 are by Bolton[12] and by Hounshell
and Smith.[13]
At IG Farben, Paul Schlack took note of Carothers’ two-
monomer polyamide and he set out to make a single-
monomer version, using a starting material with both
amine and carboxyl functionalities. Carothers had, in fact,
attempted to do this using 6-aminocaproic acid but had
achieved only a low degree of polymerization.[14] Schlack
chose instead the condensed form of this acid, namely the
ring compound e-caprolactam. These two compounds are
shown in Formula 3
On the historic date of January 29, 1938, using acid
hydrolysis of pure caprolactam, he was able to make a
polymer that could be drawn into a textile fiber of good
properties and could also be molded into a strong rod.
Because the polymer was made from a single starting
material and because that material possessed six carbon
atoms, Schlack’s polymer is called PA 6. His employers
developed a very speedy interest in the new material. A US
patent[15] was awarded on May 6, 1941. Like PA 66, PA 6 saw
immediate use as a textile fiber and as a monofilament
for brushes. The key difference in chemistry of formation
of the two polymers – the difference which avoided a
conflict of patents – is that PA 66 is formed by direct
amidation whereas PA 6 depends also on transamidation,
as shown in Scheme 2. Much of the chain growth is achieved
by the direct reaction of chain amine ends with the amide
link contained in the caprolactam molecule.
O C O
H another. Free rotation about carbon–carbon bonds, which
HO NH
NH
Formula 3. e-Aminocaproic acid and e-caprolactam.
Macromol. React. Eng. 2011, 5, 22–54
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ß 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
K. Marchildon
C O H H
N- N – (CH2)5 – C – N –
H H H
Scheme 2. Growth by transamidation in PA 6.
PA 66 is formed by step-growth polymerization. PA 6 is
formed by a combination of step-growth identical to that of
PA 66 and, to the extent that transamidation and addition of
the ring takes place, a mechanism with somewhat of a
chain-growth character. However, the latter route is still
gradual compared with the rapid reaction of highly active
chain ends in the addition polymerization of vinyl
compounds.The invention and development of PA 6 is
described by Matthies and Seydl.[16]
The polyamides of Carothers and Schlack were made
from aliphatic monomers. In the 1960–1970s, Stephanie
Kwolek of Dupont invented the polyamide fiber Kevlar1
made wholly of aromatic monomers. This material is still
probably the best known of the wholly-aromatic class of
polyamides. Compared with the best of the aliphatics, it
provides a doubling or tripling of strength and more than a
100 8C increase in the temperature of use. Realization of this
great advance required chemical and process development
of at least the same difficulty as for the original polyamides.
Working with colleagues at E. I. duPont de Nemours, Kwolek
et al.[17] devised a process for making the polymer,
formulated an optically anisotropic ‘‘dope’’ with molecular
orientation in the liquid phase from which the fiber could be
spun,[18] and produced the first fibers of this new class.[19]
Fitzgerald and Irwin[20] provide an account of the devel-
opment of Kevlar1.
Structure
Any meaningful survey of the polyamides has to take note
of the internal structures that result from the choice of
monomers: this is because structure is a prime determinant
of properties. As previously stated, the polarity of the amide
group along with the rigidity of rings (if present) – aliphatic
and, especially, aromatic – dictate the character of the
polymer. With regard specifically to the amide group, it has
a dipole moment of 3.7 D (12.3  1030 C  m), implying, if
the separation of hydrogen and oxygen is 0.34 nm as
shown in Figure 1 (taken from Aharoni[21]), that there is a
charge of 3.6  1020 C (0.23 electrostatic units) on each of
these atoms.
At least some part, and sometimes all, of the solid state
of any polyamide sample is amorphous, with the molecules
lying in random or semi-random orientation relative to one
would make this part of the structure mobile, is impeded by
the hydrogen bonding between amide groups in different
chains, as well as by bulky ring segments and/or side
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Polyamides – Still Strong After Seventy Years
C The melting temperature sets an absolute limit to
C melt-processing has to be carried out. A high melt
C
H N C from a high internal coherence and extent of crystallization,
C values of Tg and Tm as indicators of the nature of the
O H N
C C
O
0.1 nanometer
C
Figure 1. Scale schematic of hydrogen-bonded amide linkages.
substituents. The temperature at which the chains do
achieve freedom of movement, the glass transition
temperature, Tg, is an important characteristic of a
given polyamide type. Below Tg the polymer has
relatively high strength and modulus (stress/strain) and
relatively low toughness. Above Tg, assuming there is
enough of a crystalline fraction to hold the polymer
together, the polymer has significantly reduced strength
and modulus, compensated for by increased toughness.
Depending on the application it may be necessary to
employ a polymer with Tg either above or below the
temperature of use.
Depending on the regularity of the amide groups along
the polymer chains, some of the chains are drawn into
orderly regions of crystallinity. Electrical attraction
between amides in different chains (or in the same chain
if folded back on itself) pulls the molecules into hydrogen-
bonded sheets. These sheets stack up, one behind the other,
at fixed spacing, held together by van der Waal’s forces. The
exact form of the crystalline configuration has been much
studied and is found to have a number of variations,
strongly determined by monomeric content: crystallinity is
favored by regular spacing of amide groups and absence of
bulky side-groups along the chains. Crystalline regions
require temperature, a solvent or a reagent to break them
up. The melting temperature, Tm, is the temperature at
which the crystallinity loses coherence: some crystalline
forms have greater internal coherence than others and, as a
consequence, have higher melting points. For a particular
solid sample, the relative fractions which are amorphous
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and crystalline are significantly affected by the conditions
of solidification.
temperature of use, and in practical use is never closely
approached. It also sets a lower bound above which any
temperature generally correlates positively with max-
imum temperature of safe use and also, because it results
correlates with mechanical strength of the polymer.
In the survey to follow, much reference is made to the
amorphous and crystalline regions of the polyamides
discussed.
Classification of the Polyamides
Monomeric content is the most basic and important aspect
of a given polyamide. It largely determines:

cost of the polymer, based greatly on cost and
availability of the monomers;

requirements of the polymerization process;

properties and end-uses – directly and via its effect on
internal structures.
In the following survey the polymers are categorized
according to the types of monomers and combinations
thereof. Differences in properties are examined within
categories and between categories. Within each category
are identified typical property-based end uses.
The following eight groups are considered:
1. polymers from exclusively straight-chain aliphatic
monomers;
2. polymers incorporating at least one monomer that
contains one or more cycloaliphatic rings;
3. polymers incorporating at least one monomer that
contains an aromatic ring but where that ring is
separated by one or more methylene groups from the
carboxyl and/or amine end groups;
4. polymers incorporating at least one (but not
all) monomer that contains an aromatic ring that is
directly connected to the carboxyl and/or amine end
groups;
5. polymers from exclusively monomers that contain
aromatic rings, with the rings all directly connected to
the carboxyl/amine end groups;
6. polymers incorporating at least one monomer that has
one or more side substituents;
7. polymers incorporating at least one monomer that has
a special purpose such as end-capping, branching, or
chain coupling, the monomer often being of function-
ality other than two;
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8. polymers incorporating more than the minimum
number of monomers required for polymerization,
resulting in co-polymerization.
In some cases the same polymer may occur under more
than one category, with different aspects being considered.
Polyamides From Straight-Chain Aliphatic
Monomers
Polymers built from only straight-chain monomers are the
original and still dominant group. The charter members,
nylon 6 and nylon 66, i.e., PA 6 and PA 66, together
constitute about 90% of the world’s overall polyamide
usage[22] and 99% of polyamide fibers (Anton[23]). Con-
sidering first the polyamides which incorporate only a
single monomer (e.g., caprolactam), these materials are
commonly designated as AB polyamides, denoting the
opposite-end amine and acid functionality, and individuals
are referred to as PA n where n is the number of carbon
atoms in the monomer. Along with PA 6, other commer-
cially significant members of the single-monomer nylon
family are PA 11 and PA 12. PA 7 has properties that might
have let it, rather than PA 6, be the material of common use:
it makes a good fiber (Horn et al.[24]), has a much lower
equilibrium content of troublesome residual monomer
compared with nylon 6 and has a higher melting point
(230–235 8C) than nylon 6. However, it has seen limited
commercial use; it has potential niche applications because
of its piezoelectric property.[3]
The glass transition temperatures of PA 6 (dry state), PA
11 and PA 12 are all reported to be in the 40–50 8C range. The
melting points are, respectively, 225, 175–191, and 180 8C. A
long-chain single-monomer polyamide, PA 22, is men-
tioned by Ehrenstein at al.[25] as having melting point of
145 8C. The glass transition temperatures for PA 6, 11, and 12
show that, although the amide inter-attraction in the
amorphous region certainly helps to immobilize the chains
(otherwise Tg would be much lower), the along-chain
frequency of amides does not much matter. However,
Table 1 shows, via the melting temperatures, that along-
chain frequency matters a great deal to the extent and
Table 1. Melting points: straight-chain aliphatic AB polyamides.
Polyamide Amide frequency Melting point
-C
PA6 14.3 225
PA11 8.3 183
PA12 7.7 180
PA22 4.3 145
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K. Marchildon
coherence of the crystalline region. Amide frequency is
generally defined as 100 times the ratio of amide links to
total along-chain atoms.
PA 6 has frequency of 1/7 and PA 66 has frequency of 2/14
or also 1/7. The data show a large (almost linear)
dependence of Tm on this index. This relationship is typical
of such groups of polyamide homologs.
The single-monomer polyamides are treated in the
monograph by Aharoni[21] and the polymerization of the
specifically lactam-based single-monomer polyamides is
described in the text by Puffr and Kubanek.[26]
Turning to the polyamides based on a separate diamine
and a diacid, these materials are commonly designated as
AABB polyamides, denoting the diamine and diacid
components, and individuals are referred to as PA mn
where m is the number of carbon atoms in the diamine and
n is the number of carbon atoms in the diacid. They are most
notably represented by nylon 66 or PA 66, made from HMD
and adipic acid. Other commercial nylons are PA 610, PA
612, and PA 46. With two contributing monomers there are
many more possible AABB polymers than there are AB
polymers, but in practice there are about the same number
of commercial straight-chain aliphatic offerings for both
types. Compared with the AB polymers, the dry-state glass
transition temperatures for the AABB polymers are a little
higher, 40–80 8C, and, again, not much dependent on amide
frequency. Tg values for PA 46 are reported separately as
60 8C (Yamanobe et al.[27]), 75 8C (Powell and Kalika[28]), and
80 8C (Kohan[7]). Like the AB polymers, the melting points
show strong (though not exclusive) dependence on amide
frequency, as seen in Figure 2, which draws on data for 46
different AABB polyamides, much of it from the survey of 31
even-even nylons by Jones et al.[29]
Because of its relatively high melting point (265 8C), PA 66
can be considered for applications up to 165 8C and, with
appropriate additives, into the range 180–190 8C (Moore,[30]
BASF[31]). PA 46, with melting point 295 8C, is advertised as
useful to 220 8C and, for short periods, to 250 8C, with the
help of suitable stabilizing additives (DSM[32,33]).
But all of the polymers so far described have glass
transition temperatures that lie below the temperatures
420
Mel
ng Point, Tm, C
370
PA42
320
270
220 PA66
170
PA1034
120
0 10 20 30
Amide Frequency
Figure 2. Melting points: straight-chain aliphatic AABB poly-
amides.
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Polyamides – Still Strong After Seventy Years
of some desired uses, especially in automotive and
electrical applications. Also, the glass transition tempera-
tures of PA 6 and PA 66 are seriously reduced when
absorbed moisture is present. For some of today’s
critical applications that require dimensional stability
at elevated temperature, the straight-chain aliphatics –
even the most robust, PA 46 – are inadequate. On the
other hand, this remarkable ‘‘first family’’ of polyamides
has been and will continue to be adequate for most
applications.
PA 46 was introduced in the 1980s by DSM and is one of a
group of polyamides based on 1,4-diaminobutane, also
called tetramethylenediamine. An early account of the
polymerization and properties of PA 46 is provided by
Gaymans et al.[34] Heard and Mascone[35] write about the
commercialization of the product by DSM. Recently,
Yamanobe et al.[27] presented a study of the structure
and characterization of PA 46. Gaymans et al.[36] also
presented results on PA 42, showing useful properties, a
favorable dry-state glass transition temperature of 120 8C,
only moderate moisture absorption, but a high melting
temperature of 388–392 8C which makes it impractical for
melt processing. Koning et al.[37] prepared and studied PA
410 and PA 412 and foresaw potential commercialization.
In fact, a recent press release[38] from DSM says that PA 410
will be commercialized, based on the fact that the 10-carbon
diacid, sebacic, can be derived from a natural source,
castor oil.
BASF, also, has announced[39] a PA 610 that is based on
naturally sourced diacid. Similarly, PA 11 is being promoted
from the same natural source. Nieschlag et al.[40] prepared
PA 1313 based entirely on components derived from erucic
acid oils, derived from various seed plants. Evonik
Industries[41] manufacture PA 610 polymer (Vestamide1
Terra HS) of partially natural source and also a PA 1010
polymer (Vestamid1 Terra DS) with both monomers
derived from castor oil. DuPont[42] has also introduced
renewably sourced PA 610 and PA 1010 as part of their Zytel
RS1 family. Smock[43] has recently reviewed these ‘‘green’’
developments, explaining that they are based mainly on
castor oil as the source and mentioning that the Rhodia
company is also marketing a partially renewably-sourced
PA 610.
The higher polyamides have been studied, with the
objective of reducing some of the polarity and obtaining
properties somewhat closer to those of the polyolefins.
Bennett et al.[44] prepared nylon 1818. Ehrenstein et al.[25]
made PA 624 and PA 634 (6 34) to develop a compatibilizer
for nylon/olefin blends. Ehrenstein et al.[45] exploited a
source of 34-carbon diacid to make polyamides 234, 434,
834, 1034, and 1234, with possible applications as fibers and
as compatibilizers. Mutlu and Meier[46] made polyamides
220, 420, 620, and 820 from renewable sources: in this case
the diacid was unsaturated.
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Polyamides From Cycloaliphatic Monomers
Polyamides incorporating one or more aliphatic rings are
generally of the AABB type, where either the diacid or the
diamine incorporates the ring. The objective is to alter one
or both of the amorphous and crystalline regions. The
bulkiness and stiffness of the ring is expected to interfere
with inter-chain movement in the amorphous phase, thus
raising the glass transition temperature. In the crystalline
phase, the ring may or may not preclude an ordered
structure: in some applications the result is a reduction in
crystallite size to the point where the polymer becomes
transparent.
Cycloaliphatic Diacids
The cycloaliphatic or alicyclic monomer is usually the
diamine but there are a few instances of a ring-based diacid.
Bulacovschi and Simionescu[47] prepared cyclopropane-1,2-
dicarboxylic acid (CPC), 1-methylcyclopropane-1,2-dicar-
boxylic acid, and cyclobutane-1,2-dicarboxylic acid, as
shown in Formula 4. These polymers were intended to
serve as modifiers to reduce the melting point of aromatic
polymers. However, a polymer of pure CPC and HMD was
prepared and found to have melting point of 308 8C,
indicating high crystallinity. No value for Tg was given.
Schmitt et al.[48] claimed polyamides made from
1,4-cyclohexanedicarboxylic acid or 1,3-cyclohexane
dicarboxylic acid (1,3-CHDA) along with a mixture of
straight-chain HMD isomers, 2,2,4-methyl-HMD and 2,4,4-
methyl-HMD) each having three pendant methyl groups.
The irregular diamines made the polyamides fully amor-
phous and transparent. Dimensional stability was mea-
sured up to 110–120 8C, indicating an increase in Tg of over
the 40–60 8C of the straight-chain aliphatics and making
this amorphous polymer useful at normal and somewhat
above normal ambient temperatures. Campbell and Hill[49]
also made a polymer with 1,4-cyclohexane dicarboxylic
acid (1,4-CHDA), combined in this case with 1,9-nonane-
HOOC
C
a C HOOC C C
d
C COOH
C C
HOOC CH೤ C C
C C
b COOH
C COOH
HOOC HOOC C C e
C C COOH C C
c C C C C COOH
Formula 4. Cycloaliphatic diacids – a: cyclopropanedicarboxylic
acid, b: 1-methylcyclopropane-1,2-dicarboxylic acid, c: cyclobu-
tane-1,2-dicarboxylic acid, d: 1,3-cyclohexanedicarboxylic acid,
e: 1,4-cyclohexanedicarboxylic acid.
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HOOC COOH
Formula 5. 1,3-Adamantanedicarboxylic acid.
diamine possessing a pendant methyl group on the
mid carbon. Melting points were typically 270–283 8C
and dry-state glass transition temperatures 100–110 8C.
The polymer could be made into a fiber of favorable
properties. Aramaki and Maekawa[50] claimed a polyamide
in which 1,4-CHDA constituted between 10 and 80% of the
diacid segments, with an aliphatic diamine, and they stated
this polymer as suitable for automotive, electrical, electro-
nic, industrial, and domestic uses because of its resistance to
heat, light, moisture, and mechanical stress. Bennett
et al.[44] polymerized an 18-carbon diamine with the
tricyclic 1,3-adamantanedicarboxylic acid (ADA)[51] (see
Formula 5) to make a fully amorphous polymer which
melted at around 100 8C. This did not represent an
improvement over the other polymer which they made,
namely partially crystalline PA 1818, which had Tg of 45 8C
and Tm of 163 8C. The ineffectiveness of ADA in raising the
glass transition and melting temperatures to higher levels
may have been because of the extended methylene chains:
it would be instructive to try it with a shorter diamine.
Cycloaliphatic Diamines
Turning to the cyclic diamines, the simplest are the single
rings with (a) amines directly attached or (b) separated from
the ring by a methylene or higher group. The DuPont
company at one time advertised[52] availability of one of the
former type, a monomer with directly attached amines, 1,4-
diaminocyclohexane, but as a curing agent for epoxy resins.
Currently, INVISTA markets 1,2-diaminocyclohexane, as
DYTEK1 DCH-99. With its adjacent amine groups it would
not generally be suitable as a polyamide component. Under
the tradename ‘‘1,3-BAC,’’ Mitsubishi[53] markets 1,3-
cyclohexane bis(methylamine), a diamine of the latter
type with a methyl group between ring and amino group. It
too is advertised as an epoxy reagent but, in fact, Inoue and
Hoshino[54] have prepared and studied polymers of this
diamine with a series of straight-chain diacids. Endo
et al.[55] report, for the polyamide of 1,3-BAC and adipic
acid, Tg of 107 8C and Tm of 227 8C. Cyclohexanebis(methyl-
amine), both the 1,3 and 1,4 isomer, is commonly referred to
as CBMA. These structures are shown in Formula 6.
Bell et al.[56] used the 1,4 version of CBMA to make
polyamides, with very instructive results around the fact
that the saturated ring has two isomeric forms depending
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H₂C CH₂
a b
H₂N-CH CH-NH₂ H₂C CH-CH₂-NH₂
H₂C CH₂
H₂N-CH₂-CH CH₂
H₂C CH₂
H₂C CH₂
H₂N-CH₂-CH CH-CH₂-NH₂
H₂C CH₂
c
Formula 6. Single-ring cycloaliphatic diamines – a: 1,4-diamino-
cyclohexane, b: 1,3-cyclohexanebis(methylamine), c: 1,4-cyclohex-
anebis(methylamine).
on the orientation of the methyl amine groups relative to
each other. Isomeric forms of 1,4-diaminocyclohexane are
shown in Figure 3. (This isomerism is not to be confused
with the ‘‘chair’’ and ‘‘boat’’ forms of aliphatic rings. The
monomers are almost exclusively in ‘‘chair’’ form.) Bell
studied the trans form and the cis form separately and
measured the melting points of polymers with about eight
different straight-chain diacids. The trans isomer yielded
much higher values of Tm, e.g., with adipic acid, 345 8C
compared with 244 8C for the cis isomer; with dodecane-
dioic acid, 277 8C compared with 210 8C for the cis isomer.
Although no glass-transition data were given, it was
concluded from the Tm comparison that the trans isomer
makes the stronger polymer and is the preferred form. In
recognition of this preference, Butte[57] developed a method
of isomerizing cis-1,4-CBMA into trans. In the case of adipic
as the diacid, Bell et al. prepared a series of polymers with
various ratios of cis to trans-1,4-CBMA. The melting points
of the mixtures displayed the ‘‘V’’ shaped depression typical
of copolymers, with a minimum at around 80% cis. Bell
et al.[58] patented a family of polyamides made from 1,4-
CBMA and 1,3-CBMA with a wide variety of diacids. One
important and unexpected disclosure was that CBMA-
containing polymers have much greater resistance to acid
degradation than does PA 66.
The cis/trans distinction applies as well to the cycloali-
phatic diacids (already discussed) and, for instance,
Aramaki and Maekawa[50] state a trans/cis ratio of between
50/50 and 97/3 for their polymers.
A variation on 1,4-CBMA is 1,4-cyclohexanebis(ethyl-
amine) (CBEA), with two methylene groups lying between
NH₂ H
H₂N H₂N
H NH₂
H H trans
cis
Figure 3. Cis and trans configurations of 1,4-diaminocyclohexane.
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ring and amide. For polymers of adipic acid and for various H₂C CH₂ H₂C CH₂
PACM
cis/trans ratios of this diamine, Bouboulis[59] showed
H₂N-CH₂-CH CH-CH₂- CH CH-CH₂-NH₂
melting points generally about 10 8C higher than for the
methylamine analog. The polymers showed higher crystal- H₂C CH₂ H₂C CH₂
linity, lower moisture absorption, higher modulus, and H H
higher elongation and were claimed to combine the best H₃C-C CH₂ H₂C C-CH೤
properties of the polyamide of 1,4-CBMA with adipic acid and MACM
PA 66. Among his examples Bouboulis included polymeriza- H₂N-CH₂-CH CH-CH₂- CH CH-CH₂-NH₂
tion of CBEA with 1,4-cyclohexanediacetic acid, i.e., a polymer
H₂C CH₂ H₂C CH₂
in which both monomers are of the alicyclic type.
Ridgway[60] presented an extensive comparison of CBMA
H₂C CH₂ CH₃ H₂C CH₂
and CBEA with several straight-chain acids, from adipic to PACP
|
dodecanedioic. Comparing the trans versions: for equal H₂N-CH₂-CH CH-- C-- CH CH-CH₂-NH₂
overall along-chain methylene frequency, the CBEA polymers |
tended to have slightly higher melting points but Tm tended H₂C CH₂ CH೤ H₂C CH₂
to fall off rapidly as the acid length increased. For the cis
versions, the CBEA polymers had much lower melting points,
sometimes in the vicinity of 100 8C. Ridgway also presented Formula 7. Two-ring alicyclic diamines: para-bis(4-aminocyclo-
zero-humidity Tg data. Among the trans polymers the CBMAs hexyl)methane (PACM), para-bis(4-amino,3-methylcyclohexyl)-
were in the range 170–187 8C, the CBEAs in the range 135– methane (MACM), para-bis(4-aminocyclohexyl)propane (PACP).
163 8C, i.e., all favorable for high-temperature applications.
Among the cis polymers, Tg of the CBMAs were in the range for a PACM-containing polyamide with a mixture of these
130–140 8C, the CBEAs around 100 8C. All of these values are forms, Tm and Tg both increase with trans-trans fraction.
significantly higher than that of, say, PA 66, indicating the Zimmerman[6] stated that the PACM used in Qiana1 was
effectiveness of incorporating a ring into the chain. about 70% trans-trans.
The most widely used of the cycloaliphatic diamines is Hill et al.[71] studied a related dicyclic diamine, para-
para-bis(4-aminocyclohexyl)methane (PACM). An impor- bis(4-aminocyclohexyl)propane (PACP), incorporating a
tant commercial product, Rhodia’s Trogamid CX series,[61] is pair of methyl groups attached to the central carbon (also
made from the combination of PACM with dodecanedioic shown in Formula 7). Reacted with a series of straight-chain
acid, i.e., PA PACM12. This material is reported to have glass diacids, it proved to have outstanding properties of
transition temperature of 132–140 8C and, although semi- transparency, chemical and mechanical stability, and
crystalline, has crystallite size too small to scatter visible high-temperature retention of properties. With adipic acid,
light. Endo et al.[55] reported Tg of 131 8C and Tm of 246 8C. It for instance, it had a glass transition temperature of 185–
is transparent and is used for, among other things, reading 191 8C, compared with 169 8C for PA PACM6. For polyamides
glass lenses. A study of the hardness of this material was PACP12 and PACM12 the comparative Tg’s were 150 and
made by Yang et al.[62]. Patents and patent applications by 132 8C. One specific polymer was selected for detailed study,
Buehler and colleagues[63–65] claimed compositions incor- PACP combined with a 60/40 molar mixture of azelaic acid
porating PACM as a component, as well as a related cyclic and adipic acid.
diamine: para-bis(4-amino-3-methylcyclohexyl)methane One other cyclic diamine should be mentioned, the
(MACM). These double-ring diamines are shown in Formula single-ring isophorone diamine, shown in Formula 8. It is,
7. Meyer et al.[66] claimed a polymer of PACM with carefully for instance, a component of a novel series of biodegradable
selected and proportioned mixtures of diacids to yield copolyamides described by Arvanitoyannis et al.[72,73]
polymers of good transparency, chemical and dimensional Finally, consider as an alicyclic, piperazine (PIP), a
stability, low melt viscosity, and practical processing diamine that is unusual in the inability of its linkages to
temperature. In the 1970s, the DuPont company patented
a process for preparing PA PACM12[67] and for spinning it CH೤
into ‘‘ . . . a soft, bulky yarn with a high level of sheen . . .
without developing objectionable glitter.’’[68] This yarn was H₂N - CH₂ NH₂
sold under the tradename Qiana1. Blondel and Monta-
nari[69] claimed amorphous polyamides incorporating
PACM with a mixture of diacids including the aromatic TPA.
The question of isomeric form arises doubly with PACM CH೤
CH೤
because of its two rings. It can exist in three forms: cis-cis,
cis-trans, and trans-trans. Prince and Pearce[70] showed that, Formula 8. Isophoronediamine.

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form hydrogen bonds. Vinken et al.[74] prepared PA 214, PA
PIP14 and various copolymers of the two. The pure PIP14
formed a semi-crystalline polymer but the absence of inter-
chain hydrogen-bonding left the polymer with a melting
point of 142 8C, compared with 242 8C for PA 214. Whatever
stiffening of the amorphous region achieved by the ring
structure was negated by the low melting point. Katz[75]
was more successful with PIP in combination with IPA and
with TPA. Zimmerman[6] discussed piperazine-containing
polyamides.
In summary, the incorporation of common cycloaliphatic
monomers raises the glass transition temperature signifi-
cantly above that of polyamides based solely on straight-
chain monomers. This increase is ascribed to interference
with amorphous-phase chain mobility. At the same time
many of these monomers also find a place in the crystalline
structure because melting points are maintained in the
200–330 8C range. However, the use of these monomers is
complicated by the existence of the two isomeric forms, cis
and trans, one of which produces polymer properties much
inferior to that of the other. Also, as with all monomers, cost
and availability are key.
Polyamides From Link-Separated Aromatic
Monomers
Turning now to monomers containing aromatic rings, a
class of polyamides based on these monomers has been
defined as the aralifatics, in which the ring is separated on
both ends by one or more methylene groups from the amide
linkage. If the separation is by a single methylene group
then the polymer is alternatively call a polyarylamide. The
monomer has both aromatic and aliphatic character, hence
the name. The significance of the separation is that:

in the case of a diacid it precludes conjugation of the
amide carbonyl double bond with the double bonds of
the ring, and

it retains a measure of the flammability associated with
aliphatic chains.
The ring, therefore, acts in much the same way as the
alicyclic rings discussed above, i.e., contributing its bulki-
ness to the crystalline and the amorphous regions, with
effects on the melting and glass transition temperatures
and other properties.
The ring in an aralifatic can be in the diacid, in the
diamine, or in an AB type monomer. In practice, AB
monomers do not appear commercially, and the diacids
have been little studied. Two aralifatic diacids were
examined by Saotome and Komoto[76] who polymerized
them with a series of straight-chain diamines. These diacids
were para-benzenediacetic acid (BDA) and para-benzene-
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dipropionic acid – i.e., with, respectively, one and two
methylene groups separating the ring from the amide link.
The highest melting point was 259 8C for PA 6BDA and the
highest measured glass transition temperature was 110 8C.
These results did not, at that time, support pursuit of this
family of polymers. Wang and Zhang[77] have revisited
this family, polymerizing BDA (which they refer to as
p-phenylenediacetic acid) with each of 10-, 11-, 12-, and
13-carbon straight-chain diamines and obtaining proper-
ties for PA10BDA similar to those of the PPA PA 9T (to be
discussed in the next section). There are differences in the
melting points reported by these workers and those of
Saotome and Komoto.
The aralifatic diamines are the more studied and one in
particular, meta-xylenediamine, MXD, is the only commer-
cialized member of the family. It is made by Mitsubishi Gas
Chemical Company. It is polymerized with adipic acid to
make PA MXD6 and is sold as a molding compound by
Mitsubishi as Reny1 and by Solvay Advanced Polymers
(under license from Mitsubishi) as Ixef1. The polymer is
classified as a polyarylamide and is a member of the nylon
family (as opposed to the aramid family). The polymer has
modest thermal properties with Tm of 243 8C and Tg of
110 8C (dry state). In molding applications it is always
heavily reinforced, e.g., with glass fiber. Its advantages
include good dimensional stability at normal temperatures
of use and excellent surface appearance, but the major
feature of PA MXD6 is that it is a barrier to the permeation of
gases and of liquid fuels. It is sold by Mitsubishi as MX-
Nylon for protection of foods and beverages from harmful
gases such as oxygen. It is sold by Solvay as a modified Ixef1
which helps meet increasingly stringent limits on emis-
sions from fuel systems.
A very instructive ‘‘History of Nylon MXD6’’ is available
on the Mitsubishi[78] web page. It explains, for instance, that
the polymer is capable of achieving 31–33% crystallinity
but that the speed of crystallization is much different from
that of PA 66 or PA 6. Whereas the latter two polymers are
able to crystallize further even at ambient temperature (and
hence, disadvantageously, to change dimensions), PA
MXD6 is (1) much slower to crystallize even at its maximum
rate (at 170 8C), and (2) essentially unable to crystallize (and
is therefore dimensionally stable) at ambient temperature.
Sprague and Singleton[79] considered PA MXD6 as a
textile fiber candidate. However, they found several
deficiencies relative to PA 66:

less elongation for the same strength;

elastic modulus very sensitive to moisture and tem-
perature;

excessive shrinkage during exposure to boiling water.
Meta-xylenediamine is obtained from meta-xylene,
which is obtained from coal tar or petroleum as part of a
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mixture of ortho-, meta-, and para-isomers. The latter two H

are easily separated from the ortho and they are typically in CH₂ -NC- (CH₂)ೣ
O
the ratio of 70:30 meta to para. Mitsubishi[78] initially made H
MXD6
polymer with a mixture of MXD and para-xylenediamine - (CH₂)ೣ -CN- CH₂
O
(PXD), in this naturally occurring ratio, and found the
resulting PA MXD6/PXD-6 to have higher Tm (258 vs.
243 8C) and about 10 8C higher Tg than PA MXD6. But the H H
need for control over composition and over crystallization - (CH₂)ೣ -CN- CH₂ CH₂ -NC- (CH₂)ೣ PXD6
O O
rate impelled them to develop facilities for pure MXDA.
Schein et al.[80] compared polymers of adipic acid and (a)
pure MXD, and (b) a 13–15% inclusion of PXD in the dia- H H
- (CH₂)ೣ -CN- CH₂ -CH₂ CH₂ - CH₂ -NC- (CH₂)ೣ
mine. The latter polymer had Tm about 5 8C higher and some
O O
indication of better heat resistance and thermal stability. PBE6
Polymers made from pure PXD have received significant
Formula 9. Meta-xylenediamineadipamide (MXD6), para-xylene-
study, which surprisingly has not led to any commercia-
diamineadipamide (PXD6), para-phenylenebis(ethylamine)adipa-
lization, given the favorable properties of the PXD polymers. mide (PBE6).
Vogelsong[81] examined the crystal structures of polya-
mides PXD6, PXD7, PXD9, and PXD10. The even-numbered
polymers provided more clear-cut observations: Vogelsong have the disadvantage of the cis/trans duality. The
chose PXD10 for detailed study and was able to quantify the aralifatics have superior thermal properties when the para
shape and dimensions of its crystalline structure. form of diamine is used but this monomer is more difficult
Bell et al.[56] (already mentioned) in their study of CBMA to source than the meta form. The success of MXD-based
included comparisons with PXD-based polyamides. The polyamide (i.e., MXD6) arises from its combination of good
melting points of the latter were close to, but always at least economics and superior barrier properties.
10 8C lower than, the melting points of the corresponding
trans-CBMA polymer. Considering the adipic-based poly-
Polyamides of Semi-Aromatic Composition
amides, the following comparative Tm values are of
interest:
This class of monomer has no methylene group between
ring and amide link and may be called link-adjacent. The

trans-CBMA6: 345 8C.
four chief representatives are 1,3- and 1,4-phenylenedia-

PXD6: 333 8C.
mine and 1,3- and 1,4-phthalic acid. They are alternatively

MXD6: 243 8C.
called meta-phenylenediamine (MPD), para-phenylenedia-

cis-CBMA6: 242–246 8C.
mine (PPD), I or IPA, and T or TPA. There are a host of other,
more complex substances that satisfy the definition and
Ridgway’s[60] study (already mentioned) provided com-
that have been used in making polyamides, at least
parisons of PXD-based polymers with those based on CBMA
experimentally.
and CBEA, as well as comparisons with a polymer based on a
In this group of polyamides we consider an aromatic
variant of PXD, namely para-phenylenebis(ethylamine)
monomer of this type connected to one or more aliphatic
(PBE). This monomer incorporates two methylene groups
(usually straight-chain) monomers or, in some cases, a pair
between the ring and the amide link. Polymers from this
of aromatic monomers of same functionality (i.e., both
monomer had Tm about 25 8C higher than PXD-based poly-
diamine or both diacid) connected to one or more aliphatic
mers possessing the same along-chain methylene fre-
monomers of opposite functionality. This group of poly-
quency. In general they also exceeded the corresponding
amides includes, but is not restricted to, the PPAs.
trans-CBEA polymers. The measured glass transition tem-
On the basis of the predominance of diamines over
peratures of PXD and PBE polymers were similar, in the
diacids in usage among the cycloaliphatic and aralifatic
120–140 8C range, and inferior to those of the CBMA and
monomers, it might be thought that the phenylene
CBEA polymers. The three adipic-acid-containing aralifatic
diamines would be the major players in this new category
polymers that have been discussed here (MXD6, PXD6,
of polyamide. In fact, however, the path of commercializa-
PBE6) are illustrated in Formula 9.
tion has been through the aromatic acids, TPA and IPA, and
To sum up, the aralifatic polymers have properties
particularly TPA. There are four reasons:
similar to those of the cycloaliphatic polymers, in that both
are effective in raising the glass transition temperature and
the two acids are inexpensive because they are widely
both are susceptible to the effects of moisture – as are the produced, being used extensively in other polymers (e.g.,
straight-chain aliphatic polyamides. The cycloaliphatics polyesters);

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TPA and adipic acid are of similar length so, if desired,
can be co-polymerized with minimal disruption of the
solid-state crystalline structure;

terephthalic-based polymers are noted for their low
moisture absorption and for the limited effect
which moisture has on mechanical and electrical
properties;

most importantly, the double bond of the terephthal-
amide carbonyl group is in the right position to
conjugate with the double bonds of the ring, forcing
rigidity on the structure.
To pursue the third point, these polyamides may absorb
as much moisture as PA 66 (Sprague and Singleton) but
generally are reported to absorb significantly less: Chap-
man et al.[82] 0.8 as much, Glasscock et al.[83] 0.42 as much.
Jackson[84] and Nielinger et al.[85] state that glass transition
temperature is practically independent of moisture con-
tent; Chapman et al. measured a significant drop in Tg with
moisture but still much less than that suffered by PA 66. In
any case the terephthalic-based polymers are found to offer
significantly improved dimensional stability and retention
of properties in the face of varying humidity. Additionally,
Martins and Mutel[86] have claimed, for a range of 66/6T
formulations, ‘‘excellent salt stress corrosion cracking,’’
which makes these polymers ‘‘especially useful for vehi-
cular parts that are exposed to contact with salts . . . on
roadways.’’
What of the phenylene diamine polymers? PPD and MPD
were polymerized with straight-chain diacids of several
lengths by Morgan and Kwolek[87] and the polymers were
characterized. As part of the same study, phthalic-based
polymers incorporating straight-chain diamines of various
lengths were also prepared and characterized. Using these
data, Figure 4 compares melting temperatures and glass
transition temperatures for PPD-based and TPA-based
polymers, using the total number of non-ring carbons as
the basis for comparison. The two families behave similarly,
500
450
400
350
Temperature, C
300
250
200
150
100
50
0
0 5 10 15
Number of Straight-Chain Carbons
Figure 4. Comparison of polymers based on diamine and diacid
aromatics.
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K. Marchildon
with no advantage for one or the other. But Morgan and
Kwolek measured a very high 9.1 wt.-% moisture in PPD6
under conditions of saturation, indicating much higher
susceptibility to moisture than for the TPA-based poly-
amides.
As defined earlier, if a combination of TPA and IPA
residues constitute at least 55 mol-% of the dicarboxylic acid
portion of a polyamide, then the polymer is termed a PPA.
This demarcation is somewhat arbitrary but it does
correspond to the point where the aromatic diacid is
considered to exert a more significant influence on polymer
properties such as melting point. The third member of the
phthalic family, orthophthalic acid, does not enter the
picture, because polymerization is ‘‘short-circuited’’ by
imide formation which results from the two adjacently
located carboxyl groups, as explained by Katz.[75] Other
directly connected aromatic acids, e.g., naphthalenic acid
(see, for instance, Kawase et al.[88]), are not covered by the
current PPA definition but might be expected to produce
similar polymers. Yang et al.[89] presented data for
polyundecamethylene-2,6-naphthalamide (i.e., PA 11N),
showing Tg of 139 8C, Tm of 294 8C, and mechanical
properties similar to a PPA which has recently entered
the marketplace, PA 9T.
The simplest form of PPA is that formed by a single
straight-chain aliphatic diamine and a single aromatic acid,
TPA or IPA. The series of diamines, from 2-carbon to
13-carbon, with TPA has been studied in parts by various
workers: Shashoua and Eareckson,[90] Morgan and
Kwolek,[87] Wang and Zhang,[91] Wang et al.,[92] Jackson,[84]
Prochase Enterprise Co., Ltd., and [93] Novitsky et al.[94]
Melting and glass transition temperatures of these poly-
mers are shown in Figure 5.
The melting data show the odd/even difference that is
common to polymers with straight-chain monomers. The
glass transition data probably reflect the differences in
PPDn_Tm
mTPA_Tm
PPDn_Tg
mTPA_Tg
20
Figure 5. Melting points and glass transition temperatures of TPA-
based polyphthalamides.
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measurement method and conditions of the different Table 2. Melting behavior of isophthalic-based polyphthalamides
(after Gorton[99]).
sources. In any case, the Tg data all lie well above the PA 66 or
PA 6 range. The high melting points of polymers containing
Number of Melting Melting point
a diamine with less than nine carbons would make them
carbon atoms in (or softening) of corresponding
difficult to melt-process without excessive degradation.
straight-chain point of TPA-based
Nylon 9T is more tractable and has been patented by
aliphatic nylon nI polymer
Kuraray Co., Ltd (see Oka et al.[95]). Ems-Chemie AG (see
diamine, n
Kaiser[96]) have introduced a new PPA ‘‘based on long-chain -C -C
diamines’’ obtained from the castor bean plant, hence
probably 1,10-decanediamine. One advantage of these 2 292–310 455
higher diamines is low moisture absorption and conse- 3 240–288 399
quent stability of shape and of glass transition temperature. 4 230–245 433
Wang and Zhang[91] have made and tested semi-aromatic 6 170–230 370.5
polymers containing 10, 11, 12, and 13-carbon straight-
10 166–194 313
chain diamines. Jackson[84] and Liu et al.[97] have studied PA
10T. Quynn[98] spun fibers from PA 6T, following the lead of
Sprague and Singleton. However, the properties did not
justify the burden of using a solution-spinning process measured samples. The isophthalics crystallize slowly and
(with sulfuric acid as solvent). Compared with PA 66, the only under the right conditions.
new polymer was slower to crystallize, so that there was Table 3 compares properties of polyamides 66, 6T, and 6I,
further crystallization in the solid phase and also ambiguity as well as three of the polymers discussed earlier. It is seen
in crystal habit. that, while PA 6I is much weaker than PA 6T, it maintains a
Gorton[99] has measured the melting points of poly- Tg similar to that of PA 6T: its benzene ring is equally
amides made from straight-chain diamines and the other effective in immobilizing the amorphous region. It is also
pillar of the PPA family, namely IPA. Using diamines with 2, seen that the Tg’s of polyamides PXD6 and trans-CBMA6 are
3, 4, 6, and 10 carbons, he prepared polyamides 2I, 3I, 4I, 6I, in the same league as the phthalics, but these two materials
and 10I. The melting points are shown in Table 2. may be more susceptible to moisture: hence the phthalics
Two observations may be made: (1) the melting are generally the polymers of choice for dimensionally
temperatures of the IPA-based polymers are, on average, critical applications at elevated temperatures.
about 150 8C lower than those of the corresponding TPA- Although the single-diamine, single-diacid PPAs are
based polymer, and (2) a range, of considerable width, is attractive for their simplicity, most of the commercial
given for each IPA-based polymer. The former observation products are more complex. Chapman et al.[82] prepared
reflects a less organized crystalline structure, the latter PPAs from HMD and mixtures in various proportions
reflects uncertainty in the extent of crystallinity in the of TPA and IPA. Melting point dropped from 210 8C for

Table 3. Properties of some ring-containing polyamides. Ridgeway [60], Jackson[84], Nielinger et al.[85], Morgan and Kwolek[87],
Gorton[99].

Polymer Melting Glass transition Tensile

temperature temperature strength
(at 0% relative
humidity)

-C -C MPa

nylon 66 265 60 490

nylon 6T 370 125 480
nylon 6I 210 (170–230) 120–130 57–65
nylon MXD6 243 90
nylon PXD6 333 150 (extrapolated)
t-CBMA 345 190 (extrapolated)

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all-isophthalic, to 190 8C for 15:85 T:I, and then climbed
steadily as T:I ratio increased, reaching 370 8C for all-
terephthalic. A polymer of 65:35 proportions had a melting
point of 300 8C, making it practical to process, and was
studied in more detail including as a fiber, with properties
that were found to lie generally between those of PA 66 and
the polyester poly(ethylene terephthalate) (PET).
DSM[100] announced an addition to their Stanyl1 line –
‘‘ForTiiTM’’ – described as nylon 4T. Given the extreme
melting point of this compound (430 8C, see Figure 4 or 5), it
may be significant that a DSM patent (Rulkens and
Crombach[101]) claims polymers of terephthalic with
mixtures in various proportions of 4-carbon diamine and
6-carbon diamine (i.e., tetramethylenediamine and HMD).
PA 6T melts at 370 8C but, because of interference of the two
diamines in the crystalline phase, mixtures have melting
points lower than either of the pure polymers, with a
minimum (eutectic) melting point of 331 8C for a 40:60 mol-
% 4T:6T mixture.
The Oka et al.[95] patent for PA 9T covers also the
incorporation of a co-diamine, 2-methyl-1,8-octanedia-
mine, for adjustment of properties. DuPont (Glasscock
et al.[83]) makes the following family of PPAs:

a 100% terephthalic polymer with a mixture of
diamines–HMD plus 2-methylpentamethylenediamine
(MPMD);

a 100% HMD polymer with a mixture of adipic acid and
TPA, with the latter in sufficient proportion to qualify
the polymer as a PPA;

a 100% HMD polymer with a mixture of adipic, TPA and
IPA, with the sum of the latter two sufficient to qualify
as a PPA.
Further information on DuPont semi-aromatic polymers
is obtainable from Zielezinski[102]. Chen et al.[103] also claim
PPAs of single diamines (e.g., HMD) with mixtures of adipic,
TPA, and IPA. Rulkens[104] of DSM claims mixtures of TPA
and adipic acid with mixtures of 4-carbon and 6-carbon
straight-chain aliphatic diamines. Besides the manufac-
turers mentioned above there are several other makers of
PPAs of various compositions and properties, generally for
use as increasingly important members of the family of
engineering polymers.
Because of their thermal resistance the PPAs could also
find use in specialty fiber applications. Melt spinning is the
simple preferred route but Reichmann[105] pointed out that
high melt viscosity can cause excessive pressure loss and
temperature rise in the liquid streams upstream of fiber
formation. He found that addition of an alkali halide
(preferably lithium chloride or bromide) reduced the
viscosity, presumably by disrupting hydrogen bonding
within the liquid. This effect and these additives are also
made use of in the processing of the all-aromatic aramids.
Macromol. React. Eng. 2011, 5, 22–54
34
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In summary, the PPAs, often referred to as high-
temperature nylons, are now an established and important
part of the nylon plastic family. They have extended
the reach of the polyamides into difficult applications,
especially in the automotive and electronic industries.
The key, enabling monomer is TPA which is found in all
the various PPA formulations. IPA plays a supporting
role, helping to reduce melting point while at the same time
contributing its bulkiness to the immobilization of
amorphous regions and the maintenance of high glass
transition temperature.
Fully Aromatic Polyamides
Polyamides built totally (or at least 85%) from link-adjacent
aromatic monomers are the aramids. It was long recognized
that very favorable properties might accrue to a polyamide
made entirely of aromatic rings directly connected to the
amide links. These properties would result from the
stiffness and stability of the rings and the complete absence
of aliphatic content. However, making such polymers and
maintaining them in a liquid state, necessary for forming,
presented difficulties. These obstacles were overcome by
researchers at the DuPont company in the early 1960s, who
developed the polymerization process[106] and the fiber
spinning system[107] to make a polyamide (MPDI) of MPD
and IPA. McCune[108] described this product and its
properties, referring to it as PA ‘‘HT-1’’: it is now known
as Nomex1 as sold by DuPont or Teijinconex1 as sold by the
Teijin company. The initial objective for this new material
was simply to replace PA 66 in applications where
temperature, oxidative degradation, or hydrolytic attack
would destroy the mechanical properties of PA 66. McCune
stated, for instance, that, whereas the tenacity of unsta-
bilized PA 66 falls to 0 at 200 8C, the tenacity of PA MPDI
drops by only 50% at 300 8C. Also after 100 h of air exposure
at 175 8C, PA 66 loses 66% of its tenacity, PA MPDI only 4%.
And after less than 50 h in water vapor at 155 8C, PA 66 loses
50% of its strength, whereas after 400 h PA MPDI loses only
5%. Not all property comparisons are as favorable but there
were no serious negatives to impede the rapid commercia-
lization of the new product.
One important use of Nomex1 is as a replacement for the
rag paper used in electrical insulation in motors and
transformers. This new ‘‘paper,’’ formed from Nomex1
fibers, has superior electrical properties and it retains them
to higher temperature.
A very familiar usage is in fire-resistant clothing.
Nomex1 is difficult to ignite [its limiting oxygen index
(LOI) is around 30] and when it is exposed to high
temperature it tends to form a protective char rather than
volatilize. LOI is defined as the volume percentage of oxygen
in an oxygen/nitrogen mixture required to support a flame
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Polyamides – Still Strong After Seventy Years
under prescribed conditions. By comparison, a polymer
from the partially aliphatic polyamide group was found to
have LOI  22, i.e., very close to natural atmospheric
abundance.
Unlike the PPAs which require the specific inclusion of
terephthalic or isophthalic segments, the aramids con-
stitute a ‘‘bigger tent.’’ For instance, to make aramid
polyamides Yang et al.[109] used a diacid based on
naphthalene, Mehdipour-Ataei et al.[110] used a diamine
based on naphthalene, and Rabjohns et al.[111] used a
diamine based on anthracene. Benzene rings with side
substituents have been studied for possible enhancement
of properties. Some other monomers, in use or under study,
comprise two benzene rings separated by an oxygen atom
or sulfur atom or a methyl or similar group. For instance, the
Teijin company provides their Technora1 aramid based
partly on 3,40 -diaminodiphenylether. Preston[112] and
Gallini[113] provide wide surveys of the aramids and their
many types. Very recently, Garcia et al.[114] have presented
an extensive review of the synthesis, structure, and
applications of a broad range of ‘‘high-performance
aromatic polyamides.’’
The invention of Nomex1 or PA MPDI polyamide was the
first step in the aramid story. Although PA MPDI is valued
for its high-temperature retention of properties, some of
those properties, at ambient temperature, are not sig-
nificantly superior to those of PA 66 or PET. Importantly, the
tenacity of PA MPDI is about the same as that of PA 66. A
second breakthrough was needed, about ten years later, to
realize the full power of aramid technology. This step was
the invention (also by DuPont) of Kevlar1, PA PPDT, made
from the monomers PPD and TPA. The preparation and
spinning of this all-para polyamide presented a new set of
problems, which were overcome by Kwolek and co-
workers[17–19] (most notably Herbert Blades and Paul
Morgan), as described earlier. With carefully designed
spinning and drawing conditions this fiber can be made to a
tenacity more than double that of high-strength PA 66.
Wilfong and Zimmerman[115] presented the new product
(termed Fiber B) as a candidate for tire reinforcement,
superior to PA,66 polyester, rayon, wire, and glass.
Fitzgerald and Irwin[20] recounted the development and
properties of Kevlar1. The Teijin company also makes a PA
PPDT fiber and sells it under the name Twaron1.
PA PPDT sees use as a continuous fiber which can be used
to make high-strength cordage and which can be woven
into reinforcing fabric for tires. In staple form it is an
important reinforcing fiber for plastic components, e.g.,
canoes, boat hulls, rubber, and brake-shoes.
Polyamides MPDI and PPDT are similar in that both
benefit from their aromatic nature and exclusion of
aliphatic content. Both are stable and notably heat
resistant. Both require solution spinning because of their
high melting temperature. Their differences arise because
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Figure 6. Conformation of meta and para aramids.
of their respective meta and para structures. Figure 6 is
intended to illustrate the difference: the rings represent the
aromatic diamines and diacids, the connecting lines
represent the amide linkages which join the rings together.
As seen in Figure 6, successive meta rings have a ‘‘choice’’
of direction relative to the previous ring; para rings have no
such choice. Further, the benzene rings adjacent to an amide
link force the link into trans form. Consequently, even in
solution, PA PPDT molecules assume the shape of rods over
long stretches of their extent. Fitzgerald and Irwin[20] stated
that this ‘‘persistence’’ length is typically about 20% of the
length of the molecule, compared with 2% for PA MPDI and
less than 1% for PA 66. The orientation of these long sections
is random in the 20% solution in sulfuric acid from which
the PA PPDT fiber is spun but, during the draw-down and
coagulation of the spinning process, the molecules become
oriented along the fiber axis. Unlike other polyamides
(including MPDI) with their crystalline/amorphous regions,
PPDT is considered all crystalline, interrupted only by
imperfections. Unlike other fibers where subsequent
drawing increases the orientation, PA PPDT fibers can only
be modified thermally (under tension or pressure) to
increase the perfection of their crystallinity.
The crystalline structure of PA PPDT has been studied by
several workers. The sheet formed by hydrogen-bonding of
parallel molecular is shown in Figure 7.
The sheets stack one behind the other at a known fixed
distance but, with regard to the lateral positioning of
parallel sheets, two different opinions were initially
proposed. The issue was resolved by Gardner et al.[116].
Fukuda and Kawai[117] have studied changes in crystallite
size during moisture content change.
The DuPont company markets more than one version of
Kevlar1 fiber. The original two (early 1970s) were Kevlar
291 and Kevlar 491, the latter with about the same tensile
strength as ‘‘29,’’ almost twice the tensile modulus, and
about 65% of the breaking strain. These differences are
35
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H sis[121] to study the structural changes accompanying these

N
H treatments and found that, among the Kevlar products,
N Kevlar 1491 possesses both better molecular orientation
H
N and better crystalline perfection.
NH
To put some of these properties into perspective, a
NH comparison is made in Table 4 among the Kevlar1 products
NH as well as with high-tenacity industrial-grade PA 66 (using
H properties for the latter as given by Cook[122]) and with
N Nomex1 fiber.
H
N The aramids absorb appreciable moisture if left suffi-
H ciently long under high humidity. DuPont[123] reports
N
NH almost 10% by weight in Nomex1 paper at 100% relative
NH humidity, but without negative impact on dielectric or
mechanical properties. Shubha et al.[124] report around
NH
4–5% in Kevlar 491, with a disordering effect on crystalline
structure that may reduce mechanical strength and
modulus.
Two studies of interest concern the incorporation of
pendant groups onto the aramid chain. Ferreiro et al.[125]
Figure 7. Poly( para-phenyleneterephthalamide) sheet structure. added pyridyl rings to the isophthalamide component
simply in order to make the polymer more tractable and
easy to work with in the liquid phase, while trying to
thought to result from extra annealing under tension of the minimize impact on final properties. Chaudhuri et al.[126]
‘‘49’’ which has the result of making the crystal structure tried various organic and other substituents on MPD in
more perfect. In 1987 DuPont announced[118] Kevlar 1491, a order to enhance resistance to burning. They were able to
new version with 30–40% higher modulus than ‘‘49’’ and raise LOI from its value of 30 for unsubstituted polymer (e.g.,
with only about one-half the moisture absorption of Nomex1 and Kevlar1) to as high as 44 using chloro
existing aramids. Compared with ‘‘49,’’ the new fiber had substitution. Char yield deteriorated with many other
about 90% of the strength and 65% of the breaking strain: its substituted groups but remained high with the chloro
selling point is its high modulus, which is close to that of additives, equal to around 60%, the same as for the
high-tenacity graphite fibers. Dobb and Robson[119] used unsubstituted polymers. Char is desired because it insulates
X-ray analysis to compare the various commercial Kevlar1 the unburnt part of the fabric from the heat source.
and Twaron1 offerings and they determined that the An obvious question is why amino benzoic acid, meta or
crystallites in ‘‘149’’ were significantly larger. DuPont has para, is not used to make aramid polymers. Like capro-
also marketed Kevlar 9811, with modulus and breaking lactam in aliphatic polyamides, this aromatic analog
strain similar to that of ‘‘49’’ but with strength about 10– incorporates within itself all the functionality it needs to
15% higher. Rao et al.[120] confirmed the effect of heat- form the polymer. In fact polybenzoamide (PBA) has been
tensioning on fiber modulus and also examined the effect of made successfully. However, Preston[112] noted that PA
imposing pressurized steam. They also used X-ray analy- para-PBA is only about one-half as strong as PA PPDT.

Table 4. Mechanical properties of some high-strength polyamide fibers.

Fiber Tensile strength Tensile modulus Elongation to break

GPa rel.a) GPa rel.a) % rel.a)

Kevlar149 3.0 1 130 1 2.7 1

Nylon 66 1.15 8 17
Nomex1 1.4 14 10–28
Kevlar 291 1 0.5 1.5
Kevlar 1491 0.9 1.3–1.4 0.65
Kevlar 9811 1.10–1.15 1 1

a)
Relative to Kevlar491.

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Polyamides – Still Strong After Seventy Years
Consequently the commercial aramids comprise separate
diamine and diacid components.
Polyamides From Monomers with Side
Substituents
There are two distinct locations where a side substituent
may be attached: (a) the hydrocarbon part of the monomer
segment, and (b) the amide link, specifically to the nitrogen
atom of the link. If the attachment is on the non-amidic
(hydrocarbon) part then the substituent is usually part of
the monomer; if on the amide link then the substituent is
almost always added after polymerization.
Considering non-amidic locations first, some instances
have already been noted of monomers possessing a methyl
or other group attached to a methylene carbon in the main
chain. Alkyl pendant groups, whether on a straight chain or
on an aliphatic ring, are non-reactive and have little or no
effect on the progress of the polymerization. The purpose of
providing such an inert addition is generally to affect the
size and molecular packing of the crystalline regions. Other,
more reactive, pendant groups may be introduced to
provide functionality for such purposes as dyeing, flame
retardancy, and bonding to other substances. In this case
the extra chemistry may or may not affect polymerization.
Consider first the several instances of methyl group side
substituents.
Campbell and Hill,[49] already mentioned for their use of
1,4-CHDA, employed as diamine a mixture of isomers,
primarily 5-methyl-1,9-nonanediamine but also 2,4-
dimethyl-1,8-octanediamine and 2,4,6-methyl-1,7-hepta-
nediamine. The particular mixture may have been the
naturally occurring composition of the raw material from
which the diamine was produced. It is inferred that these
methyl-bearing monomers, rather than simple 1,10-decan-
ediamine, were used in order to reduce an excessively high
melting point, e.g., to the range 260–310 8C, while at the
same time retaining a favorable Tg of 90–130 8C.
Oka et al.,[95] previously cited for their PPA containing 60–
100% TPA as diacid, used, for at least 60% of the diamine
component, a mixture of 1,9-nonanediamine, 2-methyl-1,8-
octanediamine, or a combination of the two isomers. This
formulation produced good heat resistance, low water
absorption, and enhanced chemical resistance. A polymer
with diamine component comprising 80 mol-% of the
straight-chain diamine and 20 mol-% of the methyl-
substituted version had melting point of 302 8C, which
makes for practical processing.
A trisubstituted diamine is available as a commercial
product from Evonik Industries: VESTAMIN1 TMD, consist-
ing of approximately equal parts of 2,2,4-trimethylhexa-
methylenediamine and 2,4,4-trimethylhexamethylene-
diamine.[127] This monomer, combined with TPA, forms
Macromol. React. Eng. 2011, 5, 22–54
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the Evonik polymer TROGAMID1 T, or Polyamide 6-3-T as
named by Degussa, the originator of the polymer.[128] It is
amorphous, is highly transparent, and has favorable
mechanical and electrical properties. It has ‘‘good chemical
resistance compared to other plastics’’ and suffers low
shrinkage in the mold.
A patent by Schmitt et al.[48] described the use of
trimethyl HMD in combination with cyclohexane dicar-
boxylic acid (1,3-CHDA and 1,4-CHDA) and in combination
with mixtures of this acid with terephthalic and IPAs. The
polymers so made were transparent and had mechanical
properties comparable to properties of polymers in which
only TPA was used, plus the benefit of greater solubility in
ordinary solvents which is necessary for formation into
‘‘cast films, varnish films, etc.’’
Poppe and Chen[129] patented a novel crystalline
copolymer based on a mixture of HMD and trimethyl
HMD. The diacid consisted of TPA and adipic acid or TPA,
IPA, and adipic acid. Poppe et al.[130] patented a crystalline
copolymer also based on HMD and trimethyl HMD
combined with TPA alone. Both families of polyamide
enabled them to be used in critical molded objects such as
automobile hoods, lawn mower shrouds, and chain saw
guards. These are applications requiring minimum deflec-
tion at elevated temperatures.
Magat[131] sought to increase the initial modulus of
terephthalic-based polymers by providing methyl substi-
tuents on the aliphatic diamine monomer. This modifica-
tion was successful in some cases, not so in others. Based on
observation, Magat established a rule for choosing diamine.
Diamines of excessive length were not only ineffective but
also exhibited spectacular shrinkage properties, indicating
post-spinning crystallization. Magat did not test 2-methyl-
pentamethylenediamine (2-MPMD), which is now dis-
cussed.
The INVISTA company manufactures and markets a
number of products under the DYTEK1 trade name.[132]
DYTEK1A is, 2-MPMD, which has a variety of uses, one of
which is as a polyamide monomer. This molecule is shown
in Formula 10. Menczel et al.[133] prepared polyamide from
2-MPMD and TPA: they found the polymer slow to
crystallize on solidification and to possess three different
crystal forms. Villasenor et al.[134] prepared polymers of 2-
MPMD with adipic acid (six carbons) and sebacic acid (ten
carbons) and they observed quite different crystal struc-
tures from the simple polyamides 56 and 510 which also
have a 5-carbon linear diamine chain. A series of papers
from DuPont, by Stouffer et al.,[135] Keating et al.,[136] and
Starkweather et al.,[137] describe polymers of 2-MPMD in
combination with adipic acid and in combination with
dodecanedioic acid.
Although 2-MPMD has the same atomic composition as
HMD it is a considerably more complicated monomer. First,
the carbon atom to which the pendant methyl group is
37

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attached is asymmetric, so that the diamine has two stereo
isomers. Second, the molecule is unsymmetrical about the
middle carbon in the main body, so that it can enter a
growing polymer chain in two orientations. The pendant
group therefore has four possible positions in the diamine
segment in the polymer. The result is an inherently
disordered crystalline structure and one which displays
two different crystalline forms – that is, it is polymorphic.
2-MPMD finds its application, not as a stand-alone
monomer, but as a co-diamine, in combination generally
with 1,6-hexamethylenediamine, where it serves as a
crystalline modifier to reduce the temperature of melting:
see, for instance, Mok and Pagilagan.[138]
Another product from Invista is DYTEK1EP: 1,3-diami-
nopentane (or, alternatively, 1,3-pentanediamine), denoted
as DAMP in Formula 10. Like 2-MPMD it has the same stereo
and structural asymmetry. A feature is that the ethyl-
hindered amine end is only one-hundredth as reactive as
the other end, resulting in a 9:1 selectivity for the other
end.[139] As a polyamide monomer the product finds use in
‘‘coatings, adhesives, sealants, and elastomers’’ where it
modifies the viscosity and flexibility of straight-chain
diamine based polymers.
Among the cycloaliphatic monomers, Buhler and
Rytka[65] found it ‘‘an advantageous variant’’ to substitute
for PACM diamine a quantity of the methyl-substituted
diamine, MACM (see Formula 7).
An example of new functionality introduced by a
pendant group is the addition of the sodium salt of
3,5-dicarboxybenzene sulfonate[140,141] to increase the
receptivity of PA yarns to basic dyes. This additive
(see Formula 11), a functionalized form of IPA, is co-
polymerizable with other PA monomers such as adipic acid.
Gomez-Valdemoro et al.[142] studied the ion-extractive
capability of a polymer of MPD and IPA, with some of the
latter monomer supporting crown ether groups and some of
it supporting urea groups, to trap cations and anions,
respectively.
An example previously cited is the work of Chaudhuri
et al.[126] in incorporating various substituents on the
phenylene diamine ring to enhance resistance to burning.
The addition of side substituents to the amide linkage
is now considered. Le Sueur Cairns[143] obtained a patent
on the catalyzed reaction of polyamides with a mixture
C C C H
H2N C C NH2 2-MPMD
C H3
C C
NH2
H3 C C C DAMP
H2N
Formula 10. 2-Methylpentamethylenediamine (2-MPMD); 1,3-
diaminopentane (DAMP).
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38
ß 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
K. Marchildon
-CONH CONH -
SO₃⁻ ⁺Na
Formula 11. Sodium salt of 3,5-dicarboxybenzene sulfonate in
polymer.
of formaldehyde and a mono-alcohol, as shown in
Scheme 3.
This addition had the effect of making the polymer
soluble in alcohol, which facilitated its use in coatings and
films. The polymer could also be spun into a highly
extensible fiber. This N-alkoxymethyl polyamide has found
use for instance in the preservation of art objects (see
Sease[144]). The family of such polymers was denoted by
DuPont as their ‘‘Type 8.’’ Le Sueur Cairns[145] also patented
the addition of alcohols possessing a separate carboxyl
functionality, e.g., glycolic (hydroxy acetic) acid. Formalde-
hyde again provides the linkage. This family of N-
carboxyalkoxymethyl polyamides has the sometimes use-
ful property of solubility in water. The side substituent is
terminated by simply leaving the carboxyl group or by
attaching a metal atom or an ammonium group, or by
attaching an organic radical via an ester linkage. Mechani-
cally, this material can be drawn into a clear tough film.
The DuPont ‘‘Type 8’’ polymers provided the starting
point for an alcohol-insoluble hydrophilic microporous
membrane suitable for aqueous desalination. This state
was achieved by an acid-catalyzed cross-linking reaction in
which alkoxymethylated amides were joined to free
amides, as seen in Scheme 4. This polymer, surprisingly,
was significantly more heat resistant than its base resin, PA
66. The process and product are described in the patent by
Johnson.[146] In this connection, Le Sueur Cairns[143] also
spoke of the conversion of a ‘‘Type 8’’ polymer into an
alcohol-insoluble and infusible state simply by heating at a
temperature above 100 8C, presumably by a cross-linking
mechanism.
H
O \
|| + + R - OH
C=O
-C–N– /
H
O
||
-C–N– + H₂O
|
C H₂ - OR
Scheme 3. Alkoxymethylation of amide.
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Polyamides – Still Strong After Seventy Years

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O H Polyamides Incorporating Special-Purpose

|| -C – N – Monomers
-C–N– + ||
| O
Commercial polyamide products commonly incorporate
C H₂ - O R
O additives, of which there are a great variety, designed to
||
impart desired properties to the base polymer. Some of
-C–N–
these additives are amide-forming compounds themselves
|
C H₂ + ROH and they co-polymerize with the main product. Three
| classes of such materials are considered here: namely
-C–N–
||

endcappers or stabilizers;
O

branching agents;
Scheme 4. Cross-linking of alkoxymethylated amides.
chain-couplers or chain-extenders.

End capping is accomplished by including a mono-func-

Fitko and Ravve[147] used formaldehyde to attach a
phenol ring to the amide nitrogen. This ‘‘adhesive . . . graft
copolymer’’ is useful as a constituent for cements, coatings,
sealants, etc., and possibly also for easy-dyeing fibers
and for casting, potting, and molding applications. The
chemistry is shown in Scheme 5.
Haas et al.[148] took a different route from formaldehyde
intermediation and reacted amide-nitrogen directly, with
ethylene oxide. The product was N-hydroxyethyl nylon. The
side substituent could have various lengths depending on
the self-reaction of the oxide, as seen in Formula 12.
This class of polymer is considered to incorporate
desirable features of the polyamide and of the poly(ethy-
lene oxide).
O All concentrations are in units of milliequivalents per kilo-
-C–N–
|
CH₂ - CH₂ - O - ( CH₂ CH₂ O )n - H
Formula 12. Polyether attachment to amide.
tional carboxylic acid or a monofunctional amine, usually
the former, during the polymerization process. Acetic acid is
the most common for aliphatic polymers, benzoic acid is the
most common for aromatic polymers. The acid amidates
with a polymeric amine functional group (i.e., an ‘‘amine
end’’) and creates a stabilized or inert end. The effect is to
reduce the molecular weight achievable under whatever
conditions the polymerization is being carried out. Particu-
larly in batch processing, it is frequent practice to produce,
using the same equipment and processing conditions, a
range of products with different optimum molecular
weights. The conditions can be set for the product with
the highest desired molecular weight and then, for other
products, an endcapper (i.e., stabilizer) can be added. Table 5
shows the effect of concentration of an acidic stabilizer on a
polymer being polymerized to a fixed product of ends
(concentration of carboxyl ends multiplied by concen-
tration of amine ends), which is usual for batch processing.
gram of polymer. The numbers in Table 5 are based on the
following equations:
C  A ¼ PE

A ¼ CDE ¼ CDE0 S
H CH₂ OH
OH OH rhffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiiffi
DE0 þ S þ ðDE0 þ SÞ2 þ 4  PE
+ H₂C = O , C¼
2
O where C, A, and S are concentrations of carboxyl, amine,
||
and stabilized ends, and DE0 is the pre-existing difference
-C – N –
between carboxyl and amine before addition of stabilizer.
|
O CH₂
In this calculation DE0 is chosen as 30 and PE is chosen as
|| 4 000, both typical values.
+ -C-N– OH A branch point is an atom or ring from which three or
H more polymer chains emanate. Since polyamides are
generally intended to be linear polymers, such points are
Scheme 5. Phenol attachment to amide. not usually welcome and efforts are made to avoid their

Macromol. React. Eng. 2011, 5, 22–54

39
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Table 5. Effects of end-group stabilization.

Product Stabilized Difference Carboxyl Amine Total sum Mn a)

of ends, ends, S of ends, ends, C ends, A of ends,
CTA C–A CRARS

(mequiv.  kg1)2 mequiv.  kg1 mequiv.  kg1 mequiv.  kg1 mequiv  kg1 mequiv.  kg1 g  mol1

4 000 0 30 80 50 130 15 400

4 000 10 40 86.3 46.3 142.6 14 000
4 000 20 50 93 43 156 12 800
4 000 30 60 100 40 200 10 000

a)
Equals 2E6/(C þ A þ S).

creation, which always takes place to some extent through
undesirable side reactions (see for instance Schaffer
et al.[149]). Avoidance means minimizing time, temperature,
impurities, and ingress of oxygen into the production
processes. These measures tend to be successful and
unintended branching is not a major factor in most
processes.
Sometimes a controlled amount of branching is helpful in
the development of specific properties. There are several
trifunctional branching agents available for this purpose.
Workers at Imperial Chemical Industries Limited[150] used
bis(hexamethylene)triamine (BHMT) to achieve higher
receptivity to anionic (acidic) dyes in yarn. Such dyes
attach themselves to amine ends but, if an increase in the
concentration of these ends is achieved simply by
imbalancing the polymer (more diamine, less diacid), then
the molecular weight and melt viscosity decrease below
that required for spinning of the yarn. The viscosity is
regained by adding BHMT, which at the same time supplies
three amine ends per molecule. In this application the agent
is not desired to yield an actual branch, just a dye site.
Selivansky and Southern[151] claimed the use of BHMT and
also of ‘‘TAN’’ [4-(aminomethyl)-1,8-diaminooctane] to
make a yarn more receptive to the development of ‘‘crimp’’
during false-twist texturing. The alternative was to take the
polymer to a considerably higher degree of polymerization,
with attendant degradation and loss of productivity. The
molecular structures of BHMT and TAN are shown in
Formula 13.
H₂ N – ( CH₂ )₆ -N – ( CH₂ )₆ - NH₂
H cally gel-free, the significance being that induced branches
BHMT
H₂ N – ( CH₂ )೤೤ -CH – ( CH₂ )₄ - NH₂
| the polymer and create regions of non-flowable gel. The
CH₂ - NH₂
TAN
Formula 13. Amine-based trifunctional branching agents BHMT
and TAN.
Turning to carboxyl-based trifunctional branching
agents, the most widely used is trimesic acid (TMA),
consisting of a benzene ring supporting three directly
attached carboxyl groups, equi-spaced – i.e., at the 1, 3, 5
positions. Mention should be made of an isomer, trimellitic
acid, with carboxyl groups at the 1, 2, 4 positions but, rather
than a branching agent, it serves as a precursor to imide
polymerization. TMA was used by Costain et al.[152] to
increase the viscosity of a particular PA 66 feed to spinning
and molding operations, where the unbranched material
had less than optimum viscosity for spinning continuity.
As TMA content was raised, yarn tenacity and modulus
dropped but apparently stayed within the allowed limits.
Kiyotsukuri et al.[153] made polyamide film using straight-
chain diamines with carbons from 4 to 12 combined
with TMA as the sole acid. Proportions were such as to
balance the concentrations of carboxyl groups with amine
groups in each case. The polymer was cast from solution,
then further polymerized into transparent, flexible films
that were insoluble in usual polyamide solvents such
as sulfuric acid. Polymers with the shorter diamines (e.g.,
4-carbon) had the higher densities and the higher heat-
deflection (distortion) temperatures, presumably
because the benzene rings were closer together. Dai
et al.[154] co-polymerized PA 6 with TMA to produce a
portion of molecules that were star-shaped. As TMA
concentration was raised, strength, elongation, and initial
modulus all suffered but elasticity stayed about the same.
Molecular weight dropped but this may have been due to
excess of carboxyl ends over amine. Nijenhuis et al.[155]
claimed a randomly branched polyamide that is intrinsi-
added to the branches formed by subsequent high-
temperature processing have the potential to cross-link
patented formulation used an AB base polymer and the
addition of enough diacid or diamine to balance, respec-
tively, a triamine or a triacid branching agent: the specific
proportions of the components are claimed to prevent gel
formation.

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Polyamides – Still Strong After Seventy Years
A chain coupler or chain extender is a bi-functional
compound which can react with the ends of two polymeric
molecules and unite them into a single, larger molecule.
When the polymer is a polyamide, the chain extender must
be able to react with one or other of carboxyl or amine ends.
The bonds which the extender forms may or may not be
amidic. The three desirable characteristics of an extender
are:

high speed of reaction;

minimal effect on polymer properties;

absence of by-product.
The use of a chemical chain extender is an alternative to
chain-extension by further amidation in the melt or solid
phase or to the use of branching agents. One application is
in the regeneration of fiber waste, to impart sufficient
molecular weight to make it suitable for molding or extru-
sion. Two main families of extenders are the bislactams and
the bisoxazolines.
Zahr[156] claimed, in a patent, a set of three compounds:
adipoyl, isophthaloyl, and terphthaloyl biscaprolactam,
denoted, respectively, ABC, IBC, and TBC. They consisted in
each case of a central diacid segment connected on each end
by an amide link to a caprolactam ring. The chain-extending
action takes place when amine ends of the polymer break
open these caprolactam rings and form new amide
linkages. These compounds are shown in Formula 14,
where the arrows indicate the point of ring scission.
The reaction is fast, typically between 0.5 and 10 min, the
shorter times applying when catalyst and moisture are
present. With these short times the operation can be carried
out in a screw-type melt extruder with good mixing
followed by a brief holding period. There is no by-product.
The chemistry, producing only amide links, causes minimal
alteration of the base polymer although there is some
disruption to the regularity of the chains.
Stier and Schweizer[157] described a set of chain extenders
also of the bis(N-acyllactam) type, terminating like Zahrs in
a pair of caprolactam rings and having the same mechan-
C O O C
(CH₂) 5 (CH₂) 5
N C -A-C N
O O
A C
ABC ( CH₂ )₄
IBC TBC
Formula 14. Bis(N-acyllactam) chain extenders: ABC, IBC, and TBC.
Macromol. React. Eng. 2011, 5, 22–54
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www.mre-journal.de
ism of extension. The interior structure was more elaborate,
consisting of a central diamine or diol residue connected on
each end to a terephthaloyl residue which in turn supported
the caprolactam rings. The central part of the compound
could be varied, thus providing specific desired function-
ality. The amount of any of the extenders relative to the base
polymer is small, scaled to approximately the number of
polymer residual ends available for reaction. However, the
expense of constructing these chemical extenders even in
small amounts is an economic consideration.
Wang et al.[158] discussed and claimed the use of chain-
extended polyamides in medical applications, including
in their claims the family of bislactams. They note
BRUGGOLENE1 M 1251, ‘‘an extender product described
as a modified polyamide 6’’ and sold by Bruggemann
Chemical.[159] Many of their examples made use of,
carbonylbis(caprolactam) (CBC), a product of Dutch State
Mines[160] in which the two caprolactam rings are held
together by a simple carbonyl C ¼ O group. Loontjens and
Plum[161] also experimented with this extender. The
reaction of this extender with an amine end is illustrated
in Scheme 6.
Wang et al. also discuss a second family of chain
extenders, the bisoxazolines. The simplest is 2,2’-bis(2-
oxazoline) (BOZ) consisting of two five-membered rings.
Each ring can be broken by a polyamide terminal group – in
this case the carboxyl ends, as illustrated in Scheme 7. Lu
et al.[162] discuss the chemistry and the resultant polymer.
There is a decrease in crystallinity because of chain
disruption by the presence of ester linkages but the melting
point remained the same.
C O O C
(CH₂)5 (CH₂)5 + H₂ N -
N C N
O
C O
(CH₂)5
H H
N C N (CH₂)5 C N-
O O
Scheme 6. Chain extension using carbonylbis(caprolactam).
C N N C
C C + HOOC -
O O C
C N O H O
C C N CH₂ CH₂ O C-
C O
Scheme 7. Chain extension using bisoxazoline.
41

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C N N C
C C
C O O C
Formula 15. 2.2’-(1,3-Phenylene)-bis(2-oxazoline) (PBO).
A more elaborate member of the family is 2,2’-(1,3-
phenylene)-bis(2-oxazoline), supplied by Degussa and also
by DSM as ALLINCO1 PBO; use of this extender (among
others) for the recovery of PA 66 is described by Hong
et al.[163] DSM suggest a range of addition of 0.2–0.8 wt.-%,
which corresponds roughly to the amount of carboxyl ends
typically available for reaction near the end of the
polyamidation process.
Lu et al.[164] experimented with both BOZ and PBO
(sometimes called MPBO). The starting polymer, PA 6, had
carboxyl content of 71.5 mequiv.  kg1 and it was found
that the optimum addition of chain extender was 0.75–
0.77 wt.-%. Amounts in excess actually produced less
increase in molecular weight. At 240 8C, a hold time of 5 min
was found to produce most of the benefit, e.g., 90%. BOZ was
found to be more effective than MPBO. Comparative
molecular weights at 240 8C for 10 min: with no extender,
33 300; with MPBO, 38 000; with BOZ, 46 500. PBO is shown
in Formula 15.
Wang et al.[158] list several other versions of bisoxazoline
extenders. They also mention oxazines, which are 6-
membered rings, and which DSM report as a product under
development. This phenylenebisoxazine, ALLINCO1 PBOX,
is said to work much faster than PBO and two to three times
as fast as CBC.
Acevedo and Fradet[165] tested a pair of bisoxazolones as
chain extenders. Unlike the bisoxazolines, these com-
pounds react with amine ends and were found to ‘‘react
very efficiently.’’ The reaction is shown in Scheme 8.
Polyamide Copolymers
In many applications the covalently bonded amidic
structure contains a redundancy of monomeric types.
Some examples are:
H₂C N N CH₂
C R C + H₂ N -
O=C O O C=O
O lymers.
C N O H H
R N CH₂ C N
C C
C O
Scheme 8. Chain extension using bisoxazolone.
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K. Marchildon

a polymer containing two (or more) AB type monomers,
e.g., caprolactam and laurolactam;

an AABB type polymer containing more than one diacid
and/or more than one diamine;

a polymer containing a mixture of AB-, AA-, and BB-type
monomers, e.g., a copolymer of PA 6 and PA 66.
The motivation for such combinations is to obtain some
balance of properties not attainable with a single polya-
mide or attainable only with a polyamide requiring a
monomer that is not readily available. Instead a suitable
copolymer can sometimes be made from an appropriate
combination of relatively inexpensive monomers obtain-
able in bulk, such as caprolactam, adipic acid, hexamethy-
lenediamine, TPA, and IPA. Some examples have already
been discussed:

the PPAs, where the combined molar content of
terephthalic and IPA segments can be as low as 55%,
implying that the rest of the diacid content is something
else;

the inclusion of 3,5-dicarboxybenzene sulfonate as a co-
diacid, to provide a pendant sulfonic group that
increases the receptivity of PA yarns to basic dyes.
The most common and obvious way to make a copolymer
is to polymerize the monomers together and to obtain what
is generally assumed to be a random distribution of mono-
mer types along the polymer chains. Such a copolymer may
be termed a chemical mixture. By contrast, fully polymer-
ized materials are often brought together as a physical
mixture, i.e., a ‘‘blend,’’ where the components are mixed
at some level often down to the molecular but not within
the molecular chain. Both chemical and physical mixtures
have their practical and mutually exclusive applications.
However the distinction becomes blurred because, if a
physical mixture is held in the molten state and, assuming
the blend components are reactive with each other, chemi-
cal inter-reaction can take place, initially producing chains
with long sections (blocks) of one polymer and then long
blocks of the other but eventually approaching the limit of
random distribution. There is generally no incentive, and
good reason not, to allow time for this final state to be
reached, but it is common for physical blends to undergo
some small extent of cross-reaction in the normal residence
time of melt processing. Thus the distinction is made
between random copolymers and block copolymers. Ken-
ney[166] compares and contrasts the usefulness of these two
entities. The present review deals only with random copo-
Copolyamides comprise exclusively polyamide-forming
monomers, i.e., amino carboxylic acids, diacids, diamines,
and simple derivatives thereof. Polyamides can also form
copolymers with other monomer types that happen to
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Polyamides – Still Strong After Seventy Years
possess functional groups that can react with amine or acid
ends: some of the resulting linkages are shown in Formula
1. So, polyester amides (PEAs), polyether amides, polyur-
ethane amides are all found in commercial uses. Similarly,
physical blends are often formed by polyamides with other
polymeric species with which they do not react.
These combinations may be summarized as follows:

random copolymers of polyamides with polyamides;

blends of polyamides with polyamides, generally as
block copolymers;

copolymers of polyamides with non-polyamides;

purely physical blends of polyamides with non-poly-
amides.
The present discussion concerns materials mainly of the
first group and, to a limited extent, the third. In this paper
there is no discussion of block copolymers or of physical
blends, although they certainly constitute important com-
mercial offerings of the plastics industry.
The discussion is grouped as follows:

full-range studies, where the properties of a copolymer
pair are measured over the complete range of propor-
tions (0–100% of each polymer);

modification by co-polymerization, where the properties
of a homo-polymer are adjusted by addition of a second
polyamidic component;

low-melting copolyamides, suitable for adhesives,
coatings, or transparent applications;

copolymerization with non-amidic monomers or
polymers.
Full-Range Copolyamide Studies
It is appropriate to begin with combinations of the two
main polyamides, PA 6 and PA 66. Allen[167] presents a pair
of curves for the melting points of such mixtures, as seen in
Figure 8.
260
Mel
ng temperature, C
240
220
200
180
160
140
120
100
0 20 40 60 80
Wt.-% Nylon6
Figure 8. Effects of random and block copolymerization on melt-
ing points of the system PA 6/66 (Allen).
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The curve marked ‘‘Tm, rand’’ shows values for fully
randomized along-chain distribution of monomer seg-
ments and it reveals a marked depression, below the value
even for the lower-melting component, at approximately
equal concentration of the two components. This behavior
is common to random copolymers and reflects the mutual
disruption of crystalline structure by the two polymers. For
comparison, the curve marked ‘‘Tm, block’’ is taken from the
patent by Coffman[168] and is for PA 6/PA 66 mixtures that
have been formed by blending the homopolymers and
allowing sufficient time for them to react into a block
copolymer but not to randomize. This block copolymer
shows a monotonic rise in Tm from the lower melting to the
higher melting polymer; as stated, block copolymers will
not be discussed.
Harvey and Hybart[169] further explored this copolymer
system in its randomized state, measuring melting points,
crystallization rates, and densities for 12 different propor-
tions, from 100% PA 66 to 100% PA 6. Crystallization was
found to require lower temperatures (i.e., to be more
difficult) for the mixtures. Extent of crystallization was
inferred from density, crystalline regions being more dense:
although the densities of the two pure components differed
by only 0.006 g  cm1, the density of the 50:50 copolymer
fell by 0.03, indicating a major loss of crystallinity. Figure 9
shows the variation of crystal fraction as a function of
composition: the curve should be compared with the curve
for Tm of random copolymer in Figure 8, with which it is very
similar in shape. In Figure 9 composition is expressed as
mol-% of PA 6, where mole fraction is here defined as
concentration within the polymer of caprolactam residue
divided by the sum of concentrations of residues of
caprolactam, HMD, and adipic acid.
Suehiro et al.[170] obtained the same general results for
this copolymer and found that subsequent annealing
brought little change. They also examined the system PA
6 with PA 68 and made similar findings.
Zilberman et al.[171] made an extensive study of the
system nylon 6/nylon 69. The variation in four parameters
are summarized in Table 6, all indicating lower crystallinity
%crystal.
65.00
60.00
55.00
Tm, block 50.00
Tm, rand. 45.00
40.00
35.00
100 0 20 40 60 80 100
Mol-% Nylon 6
Figure 9. Crystallinity of PA 66/6 random copolymers (Harvey and
Hybart).
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 K. Marchildon

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Table 6. Loss of crystallinity in the copolyamide system PA6/PA69 (after Zilberman et al.[171]).

Sample Melting temperature Heat of fusion Average crystal size Crystallinity

-C J  g1 nm %

pure nylon 6 221 60 14.1 42

pure nylon 69 211 46 8.5 34
a) b) c)
minimum value 126 15 5.9 17d)

a)
At 55 wt.-% PA 69; b)At 70 wt.-% PA 69; c)At 56 wt.-% PA 69; d)At 55 wt.-% PA 69.

in the polymer. Conclusions were drawn about the nature
and inter-mingling of crystal forms, and observations were
made of spherulite formation.
Johnson et al.[172] co-polymerized PA 6 and PA 7 and
concluded that the components were randomly distributed.
Pure component melting points were measured as 219 and
222 8C, respectively; for 45:55 mol-% mixture of PA 6 to PA 7
the melting point went through a minimum of 151 8C.
One of the main reasons for copolymerization is to alter
mechanical properties, often to sacrifice tensile strength
and modulus in favor of gaining toughness. The powerful
effect of mixing of monomers is illustrated by the results of
Garner and Fasulo[173] for the combination of PA 6 and PA
12, polymerized together from a mixture of caprolactam
and laurolactam. Data taken from their table of Tensile and
Impact Properties are reproduced in Table 7. Goodman and
Kehayoglou[174] also worked with PA 6/12 copolymers and
obtained similar results.
All of the above binary copolymers comprise compo-
nents which, in their pure state, have crystal structures that
happen to be different in nature from each other.
Kehayoglou and Arvanitoyannis[175,176] studied the ran-
dom copolymer of PA 8 and PA 12, a pair of components
which in their pure state have similar crystalline structures,
differing only in the lengths of the monomeric segments.
However, the mismatch of segment lengths was enough to
cause crystalline disruption and a bottoming of melting
points (127 8C for a 50:50 molar mixture compared with
197 8C for pure PA 8 and 176 8C for pure PA 12). On the other
hand there was no minimum in density, only a smooth
monotonic variation between the values of the densities of
the pure components. The densities were subjected to a
rigorous interpretation to estimate the fraction of crystal-
linity: the fraction was indeed suppressed but not nearly to
the extent of some of the other copolymer systems, thus
indicating that the crystals were able to partially accom-
modate the different monomeric lengths but still were
weakened and more easily melted than the crystals of
either parent polymer.
Stouffer et al.[135] copolymerized PA 66 with PA D6, where
‘‘D’’ is the designation for 2-MPMD. As was previously
noted, this isomeric form of hexamethylenediamine has an
asymmetric carbon atom and therefore two chiral forms.
Additionally, the methyl side group is situated at unequal
distances from the two ends, so that the monomer adds to a
growing chain in two different ways. The result is that PA
D6 crystallizes much more slowly than PA 66 and, as
Keating et al.[136] found, it has two different forms of

Table 7. Mechanical properties of PA6/PA12 copolyamides (after Garner and Fasulo[173]).

PA6:PA12 Tensile strength Tensile modulus Elongation at break Impact strength

mol-% MPa GPa % J  m1

100/0 89 3.2 21 20
90/10 66 2.7 60 55
80/20 38 1.8 160 110
70/30 51 0.63 580 700
60/40 53 0.45 530 no break
50/50 50 0.50 560 no break
40/60 43 0.55 500 no break
30/70 49 0.72 270 350
20/80 – – – 160
0/100 – – – 60

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Polyamides – Still Strong After Seventy Years
crystals. In 66:D6 copolymers containing up to well over
50% D6 the dominant crystal form was still that of 66. Over
all ranges there was no evidence of coexistence of the two
nylons within the same crystal structure and, because of
this fact, the equation of Flory[177,178] was expected to be
followed. This relationship predicts the decrease in melting
temperature of a semi-crystalline polymer diluted with a
non-cocrystallizing copolymer.
ðTm Þ1 ¼ ðTmo Þ1 RðDHL Þ1 lnðXÞ
where Tm is the melting temperature (K), Tmo is the melting
temperature of the pure polymer (K), R is the gas constant
(8.314 J K1 mol1), DHL is the heat of fusion of the repeat
unit of the starting semi-crystalline polymer (J  mol1),
where a mole here equals one repeat unit (weighing, for PA
66, 226 grams), and X is the mole fraction of the semi-
crystalline polymer (in this case, PA 66).
A plot of inverse temperature against logarithm of X
produced a straight line and indicated a DHL value of about
42 000 J per repeat unit or 188 J  g1, which agrees well with
the value 190 obtained by a different means by Stark-
weather et al.[179]
A copolymer of both scientific and commercial interest is
the combination PA6I/6T. At a diacid ratio of 2:1 the
material is fully amorphous and is a commercial product
sold, for instance, as DuPont Selar1PA 3426 and
described[180] as a ‘‘ . . . resin which exhibits superior
transparency, good barrier properties to gases, water,
solvents and essential oils and high temperature structural
properties which make it suitable for consideration in a
number of packaging applications.’’ Chapman et al.[82]
made a more extensive study of the 6I, 6T copolymer
system, with a view to finding a polymer, based on
inexpensive monomers, for a fiber that would combine
some of the best features of PA 66 (e.g., good dyeing,
moisture regain) with those of PET (e.g., dimensional
stability). Melting point of the random copolymer went
through a minimum at 85% 6I, as seen in Figure 10.
400
Mel
ng temperature, C
350
300
250
200
150
0 20 40 60
Percentage 6I
Figure 10. Melting behavior of the copolymer system PA 6I/6T
(Chapman et al.).
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Below 50% 6I fraction the polymer developed significant
crystallinity after spinning and drawing. In order to
maximize the terephthalic fraction but still maintain a
workable processing temperature, a 35:65 ratio of 6I to 6T,
with melting point 300 8C, was chosen for evaluation.
Properties examined and compared with PA 66 and PET
were tenacity, modulus, elongation, elastic recovery,
shrinkage, moisture uptake, dyeability, toughness, tire
flatspotting, cord-to-rubber adhesion in tires, and textile
wrinkle recovery. In some case the new product met its
objective: dyeability and moisture uptake closer to poly-
amide than to PET, modulus higher than both polyamide
and PET, glass transition in the same range as PET (and
higher than PA 66), flat-spotting closer to PET (i.e., low) than
to PA 66. However, the copolymer had lower tenacity than
PA 66 and PET, lower recovery from strain, and poorer
wrinkle recovery. The net balance of disadvantages and
advantages, along with the need to process at 15–20 8C
higher temperature, appear to have stopped any commer-
cialization.
The Rulkens, Crombach DSM patent[101] provided melt-
ing point data across the whole range of proportions of the
system PA 4T/6T, as shown in Figure 11. The two
components in pure state would require melt processing
at temperatures which appear impractical from the
standpoint of thermal degradation. However, the 60 mol-
% 6T copolymer has a melting point of 331 8C, which brings
it into a possibly processable range.
Generally speaking, the incorporation of an aromatic
monomer into an aliphatic polymer has the effect of raising
the glass transition temperature but lowering the melting
point due to disruption of crystallinity. While the latter
effect may be beneficial to the ease of melt processing, it
forces down the upper temperature of use of the material.
Consequently it was a significant discovery by Edgar and
Hill[181] that polyamides 66 and 6T form copolymers with
no minimum in melting point: Tm rises smoothly from
that of PA66 (265 8C) to that of PA 6T (367 8C) and Tg
rises smoothly from that of 66 (e.g., 60 8C) to that of 6T
(125–180 8C). The diacids adipic and terephthalic are said to
be isomorphic because the two polymers, 66 and 6T, are
Mel
ng temperature, C
440
420
400
380
360
340
320
80 100 300
0 20 40 60 80 100
Mole percent 6T
Figure 11. Melting points of PA4T/6T copolymers.
Macromol. React. Eng. 2011, 5, 22–54
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thought to co-crystallize without significant disruption of
the crystal structure. This effect relies on two factors: the
similarity in lengths of the residual segments of adipic and
terephthalic, and the force of hydrogen bonding that
overcomes the differences in shape and orientation of the
two segment types. The latter point is evinced by the fact
that in polyester, with no hydrogen bonding, adipic and
terephthalic do not form an isomorphic pair. Yu and
Evans[182] pursued the examination of polyamide iso-
morphs and found that other straight-chain aliphatic
diamines besides hexamethylenediamine worked equally
well with these two acids. However, the isomorphicity was
destroyed when meta-xylene diamine or a diamine with
alkyl side substituents was used. Levine and Temin[183]
listed other isomorphic systems:

sebacic and para-benzenedipropionic acids (in combi-
nation with hexamethylenediamine);

octamethylenediamine and 1,4-bis(b-aminoethyl)ben-
zene (in combination with adipic acid);

bis(3-aminopropyl) ether and heptamethylenediamine
(in combination with adipic acid).
They produced two new isomorphic pairs: epsilon amino
caproic acid (i.e., PA 6 monomer) with para-aminocyclohex-
ylacetic acid; and epsilon amino caproic acid with para-
aminomethylbenzoic acid. They also experimented with
the meta forms of the two co-acids and found them not to
form isomorphs.
The discovery of the ability of adipic acid and TPA to form
copolymers with no loss of high-temperature properties
and improvement of low-temperature properties (espe-
cially Tg) has led to the class of PPA polyamides. In some
formulations part of the terephthalic is replaced by IPA,
which has no isomorphic capability but which raises glass
transition temperature equally well. This addition helps to
moderate the melting point. Another useful component is
2-MPMD (see Formula 10), added to replace part of the
hexamethylenediamine in order to disrupt some of the
crystallinity and again restrain the melting point to a
workable range. In this case the adipic acid component can
be eliminated, allowing terephthalic (with or without
isophthalic) to be used alone. In their patent, Mok and
Pagilagan [138] have explored various combinations of these
ingredients. Leboeuf[184] has produced a high-temperature
copolymer from HMD and 2-MPMD, with TPA and an
aliphatic diacid, claimed to have improved shrinkage and
mechanical properties.
Modification of Homo-Polymers by Copolymerization
This topic follows naturally from the above full-range
studies. However, in contrast to the full-range studies,
many of which were mainly scientifically motivated, the
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K. Marchildon
modification studies are often driven by a need to obtain
specific changes to a polymer’s properties. A typical
example is the work of Morhenn et al.[185] who found
that the dye receptivity of PA 6 fiber can be
improved by copolymerization with a small amount
(20–25 mol-%) of a combination of PA 66 and either
polyamide 11 or 12.
Men and Rieger[186] studied several aspects of the
copolymer of polyamides 6 and 66, in molar ratio 4:1.
The material showed moderate differences from pure PA 6
in the form and quality of its crystalline fraction, a
reduction in melting point to 199 8C (from 220–225 8C of
pure PA 6), and little change in glass transition temp-
erature – which is not surprising since the two components
have similar Tg’s. Jo and Baik[187] and Baik and Jo[188]
widened the consideration of PA 6 modification by pairing
it with each of several different copolymer partners:
polyamides 66, 6T, 6I, PXD6, MXD6, and MXDI (where
PXD and MXD are para and meta xylene diamines), each at a
number of molar contents, some up to 33%. As above, the Tg
with PA 66 was little changed, but it was increased by
pairing with the aromatic monomers due to hindrance of
chain mobility in the amorphous phase. The important
point was established that the extent of co-crystallization
varied with the nature of the second polymer. It was
concluded that PA 66, because it is similar in shape and
dimensions to PA 6, enters into the crystal domain,
although distorting and weakening it and causing a
decrease in melting point. But polyamides 6T and MXDI
each remain almost wholly in the amorphous domain,
leaving only the PA 6 to crystallize: with heavy loading of
the second polymer, the PA 6 segments are separated from
one another and able to form only small and sparse
crystalline zones, causing an even bigger drop in melting
point. The other co-polymerizing additives – MXD6, PXD6
and 6I – showed evidence of partial inclusion in the crystals.
Jo et al.[189] measured thermal shrinkage in oriented films
made from of PA 6 with from 4 to 33 mol-% of PA 66 and also
films made from PA 6 with from 2 to 13.5% PA PXD6.
Shrinkage is a key property for end-use applications. At low
temperatures, 20–120 8C, the 66-containing films shrank
with temperature to an extent independent of composition.
But the shrinkage of the PXD6-containing films fell
significantly with PXD6 content. At higher temperature,
up to near the melting point, both families of copolymer
displayed increased shrinkage with co-additive content, the
PXD6-containing films more so than the 66 films. The
favorable low-temperature results for PXD6 were explained
as due to the hindering by PXD6 of amorphous-domain
chain mobility, because initial shrinkage takes place due to
molecular movement in this region. The high-temperature
results were explained as due to weakening of crystallinity,
PA PXD6 being less able than PA 66 to co-crystallize with
PA 6.
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Polyamides – Still Strong After Seventy Years
In developing packaging films, Scarfato et al.[190] pre-
pared copolymers of PA 6 with 5 wt.-% of (separately) four
different co-components: polyamides 6I, 66, 69, and a
cycloaliphatic-aromatic polyamide. All melting points were
slightly reduced, all glass transition temperatures were
slightly raised (except for the 66 copolymer). All materials
showed higher elongation-at-break than PA 6 and the two
aromatic-containing co-additives raised the tensile mod-
ulus by about 30%. Most important, the aromatic-contain-
ing copolymers, especially that with PA 6I, showed a major
improvement in barrier to the transfer of carbon dioxide,
oxygen, and nitrogen.
Rusa and Rusa[191] sought to increase the impact
resistance of PA 6 by copolymerizing caprolactam with
laurolactam, the precursor of PA twelve (PA 12). This
operation was carried out by anionic polymerization.
Concentrations up to 50% by weight of PA 12 were tested.
It was concluded that only the PA 6 crystallized, so that
there was a decrease in percentage crystallinity from 52%
for pure PA 6 to 20% for the 50:50 mixture and a decrease in
melting point of 15–20 8C. Impact strength, as measured by
the Notched Impact procedure, indeed rose, approximately
linearly with weight % PA 12: as little as 13 wt.-% of PA12
doubled this indicator of toughness. This improvement was
at the expense of flexural modulus which fell 27%.
The above studies all had PA 6 as the base polymer.
Turning to PA 66, the reasons for modifications are
somewhat different from those of nylon 6. The melting
point is about 40 8C higher and the susceptibility (because of
the adipic acid segments) to thermal degradation is higher.
Like nylon 6, pure nylon 66 is sometimes overly stiff and
unnecessarily strong for some applications. The crystal
fraction in nylon 66 tends to be greater than that in nylon 6.
DeWitt[192] found it helpful to co-polymerize succinic acid
with PA 66 in a fiber –spinning process. Pressure gradient
through the molten-polymer supply piping was reduced,
allowing either higher throughput or higher molecular
weight to be implemented. Dewitt also claimed improve-
ments in yarn tenacity and decreased spin breaks. It is
uncertain to what extent succinic acid acted as a
comonomer, since it is also known to cyclize into an imide
which then acts as a mono-functional chain-stopper.
Hammond and Marks claimed reductions in gelation
propensity when they copolymerized various alternative
diamines with the HMD of nylon.66 These comonomers
were ethyltetramethylenediamine,[193] trimethylenehexa-
methylenediamine,[194] and pentamethylenediamine.[195]
Because of the high crystallinity of nylon 66 it has
sometimes proved energy-intensive and time-consuming
to achieve good dye penetration. Kobsa and Windley[196]
found that the addition of 6–12% by weight of nylon 6 as a
copolymer component resulted in a large reduction in
energy requirement. In the same vein, the INVISTA
company markets DYTEK1A (i.e., 2-MPMD) as a monomeric
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additive for fibers, with the benefits[132] of ‘‘Less crystal-
linity, fewer line breaks, more flexibility, less gel, longer
pack life, lower melt and quench temperatures, improved
water absorption, ease of dyeing, softer feel, and abrasion
resistance.’’
Kudo et al.[197] copolymerized PA66 and PA PPDT in
various proportions up to 30 mol-% PPDT. As PPDT was
increased, an initial decrease in melting point was followed
by a rise back to that of pure PA66. Partial co-crystallization
of the four components (66, 6T, PPD6, and PPDT) was
postulated. The authors suggested that such a copolymer
could be commercially attractive because of its strength-
giving crystallinity, its moderate melting point, and its
likelihood of being more thermally stable than pure PA 66.
Besides PA 6 and PA 66, other polyamides are also
beneficially modified by co-addition. In the work of Zhang
et al.[198] PA 11 was the base resin and PA 66 was introduced
as a modifier. These two polyamides are not fully miscible
when blended, so instead the 66 polymer was dissolved into
11-aminoundecanoic acid monomer at the start of PA 11
polymerization. The result was a random copolymer and,
not only was the question of immiscibility circumvented,
but the two polymers entered into co-crystallization.
Melting point was depressed from 202 8C for pure PA 11
to 192 8C for 5 wt.-% of PA 66 addition and to 181 8C for
10 wt.-% addition.
Low-Melting-Point Copolyamides
This class of polyamide must suffer enough disruption of
hydrogen bonding to significantly lower their crystallinity
and melting point but retain enough internal bonding to
keep them strong enough for their intended end use. These
requirements are in contradiction to each other but three
ways have been found to jointly satisfy them:

in some of the amide links, replace the hydrogen atom
with an organic group–already discussed in the Section
’Monomers with Side Substituents’;

use ‘‘dimer acids’’ as the diacidic component – a common
component of adhesives (see, for instance, Johnson
et al.[199]);

co-polymerize a mixture of polyamides – the subject of
the present discussion.
Zytel 611 was an early offering of the DuPont company
and consisted of a terpolymer of polyamides 6, 66, and 610
(see Kohan[200] and see Brubaker et al.[201]), probably in the
molar proportions 40:30:30 (see Larose[202]). An important
feature of this copolymer is its solubility in alcohol: Larose,
for instance, was able to prepare a solution in ethyl alcohol.
Beachell and Carlson[203] used a powerful alcoholic solvent
to dissolve nylon 6, 66, and 610 individually and also Zytel
611 and found Zytel 611 to dissolve the most readily. An
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important use of Zytel 611, applied as a solution, is in
conservation, where it is used to protect paper and other
art objects.[204,205] (Another alcohol-soluble polyamide, N-
methoxymethyl nylon, that was mentioned earlier in the
Section ’Monomers with Side Substituents’, is also used for
this purpose.)
No melting point is given for Zytel 611 because, being
completely amorphous, it has no sharp solid/liquid
transition. However, Davis[206] obtained some revealing
results working with a similar terpolymer, ‘‘RDG 114T,’’
from Elf Atochem, consisting of polyamides 6, 66, and 612.
Quenching this polymer from the melt at usual speeds
(seconds) produced a verifiably amorphous solid. However,
the glass transition temperature is 20 8C, so that even at
normal temperatures of use the polymer has the potential
to develop any latent crystallinity–which is what occurred.
When the process was accelerated by annealing at 75 8C
then, upon reheating, a strong endothermic peak (i.e., at
melting point) developed at 107 8C. Crystallinity was
estimated at 10%. Presumably similar results would be
obtained with Zytel 611. Some generalizations may be
made from this finding. When a copolyamide is made from
the combination of PA 6 and PA 66 alone, the minimum
melting point is around 160 8C. It is considered that a low
level of crystallinity remains, due to similarity in dimen-
sions of the monomeric components. When a third polymer
is added, e.g., PA 610 or PA 612, it is enough to make the
material completely amorphous under normal quench
conditions. However, there still remains a potential for
long-term crystalline development, a possibly de-stabiliz-
ing factor in end uses.
A second (and wide-spread) use for low-melting poly-
amides is as hot-melt adhesives. Again a disruption of
hydrogen bonding is sought. Horn et al.[207] achieved this
end by combining two means: co-polymerization, and use
of secondary amines to produce amide links with no
hydrogen-bonding capability. The copolymer components
were PA 6 (or, alternatively PA 12 or other mono-monomeric
polyamide) and a di-monomeric polyamide (AABB type)
consisting of an aliphatic or cycloaliphatic diacid and a
diamine combination containing some fraction of diamines
with secondary amines. For this purpose, piperazine (see
Formula 16) was used. This product showed good strength
and resiliency over a wide range of temperature and was
claimed as suitable for bonding in furniture making and in
HN NH
O -C – N –
C N N C
O OH
Formula 16. Piperazine and non-hydrogen-bonding amide links.
Macromol. React. Eng. 2011, 5, 22–54
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home construction. Chen et al.[208] also experimented with
piperazine in hot-melt adhesives and found, as they
increased its content, that it lowered both the crystallinity
and the glass transition temperature.
Hot-melt adhesives are used in the manufacture of
clothing, where they have to satisfy a number of require-
ments:

high bond strength;

resistance to dry-cleaning solvents;

resistance to washing temperature up to 80 8C;

melting point below 115 8C, and preferably less, to allow
application to temperature-sensitive fabrics.
Raabe and DeJong[209] copolymerized PA 6, PA 11, and PA
12 (individually) with HMD polymers of various aliphatic
diacids to achieve polymers with melting points as low as
90 8C. No component accounted for more than 40 or less
than 15 wt.-% of the copolymer. Poessnecker et al.[210] co-
polymerized polyamides 6 and 12 and a mixture of diacids
and diamines to achieve melting points in the range
79–121 8C. The diacids that were tested included both
aliphatic and aromatic; the diamines included hexamethy-
lene, 2-MPMD and piperazine.
Also concerned with adhesives for use with fabrics,
Besshaposhnikova et al.[211] started with a copolymer of PA
6 and PA 66 melting at 160–165 8C, then attempted to lower
the melting point by adding agents to interfere with amide-
link hydrogen bonding. The starting material consisted of a
60:40 wt.-% mixture of caprolactam and PA 66 salt. Several
chemicals were able to lower the melting point but only to
around 140 8C: further addition began to weaken the peel
strength of the adhesive. Among the additives were castor
oil, acetic anhydride, and formaldehyde. The last named
would be expected to react with an amide link in the
manner shown in Scheme 9.
Two patent applications by Degussa AG claimed
compositions for transparent decorative films suitable for
vehicles, sporting goods and other items. These films melt
mainly in the range 180–195 8C, which lets them tolerate
thermal processes such as printing. They are resistant
to scratches and to weather and solvents. In one of
these applications, Wursche et al.[212] claimed copolymers
of metaxylenediamine and higher straight-chain aliphatic
diacids (ten carbons and higher), sometimes with a small
O
H H ||
O \ / -C – N –
|| + C |
|| HCH
H |
O
Scheme 9. Methoxy-substituted amide link.
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Polyamides – Still Strong After Seventy Years
amount of paraxylenediamine also present. In the other
application, Baumann et al.[213] claimed copolymers
comprising HMD or decamethylene diamine plus a
cycloaliphatic diamine (with one or two rings) with sebacic
or dodecanedioic diacid. One of the features of these
materials is that, unlike the lactam-containing copolymers
with which they compete, they do not leave monomer
deposits.
Copolymerization with Non-Amidic Monomers
Copolymerization of polyamide monomers with non-
amidic monomers takes advantage of valuable properties
that polyamides bring to the partnership. The amide
linkage, with its hydrogen-bonding capability, can supply
strength, crystallinity, thermal stability, and resistance to
chemical attack, while leaving its non-amidic partner to
supply the properties for which it has been chosen.
Copolymerization is made possible typically by reaction
of carboxyl ends with the hydroxyl ends of a polyester or of a
polyether or by reaction of amine ends with the isocyanate
ends of a polyurethane. Four applications are examined
here:

Copolymerization with polyester to make biodegradable
polymer.

Use of polyamide as hard segments in thermoplastic
elastomers (TPE).

Inclusion as part of a liquid crystalline polymer.

Provision of sites for acid-dyeing.
To quote Garg et al.,[214] ‘‘Aliphatic PEAs have gained
much interest as potential candidates for biomaterials as
they combine favorable properties of polyamides (high
mechanical and thermal stability) and polyesters (higher
degradation rate through hydrolytically labile ester
groups).’’ One such PEA is a copolymer of 1,4-butanediol,
adipic acid, and 6-aminohexanoic acid, typically with 40%
ester bonds and 60% amide bonds. The product was desig-
nated as BAK, based presumably on the names of its com-
ponents: Butanediol, Adipic, Kaprolaktam (i.e., e-caprolac-
tam). Wiegand et al.[215] studied the full degradation of BAK
1095 by microorganisms. Ferre et al.[216] studied degra-
dation by warm water and by enzyme catalysis. They also
examined replacement of the adipic by glutaric or succinic
acid. For reconstructive surgery, Hemmrich et al.[217]
examined the promising use of non-woven fabric formed
from a PEA comprising these three components. A second
product, BAK2195 consisted of HMD, adipic acid, and 1,4-
butanol. However, Bechthold et al.[218] reported that ‘‘pro-
duction of BAK was stopped in 2001 due to economic
reasons.’’ In these PEAs the distribution of the various
monomer segments may have been completely random.
Garg et al.[214] investigated the effect of incorporating the
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amidic component in the form of pre-formed dimers that
allowed sequences of one, two, or three amide groups in a
row. Co-polymerized with an adipic-butanol polyester, the
length of these sequences had a major effect on the crystal-
lization of the copolymer. In the three-adjacent-amide
copolymers the crystals consisted mainly of nylon; in the
two-amide copolymers nylon and polyester co-crystallized;
and in the single-amide case the polyester alone crystal-
lized. Since the objective of including polyamide is to take
advantage of its strongly bonded crystals it would seem
that the long amide sequence is preferred. Subsequently,
Garg et al.[219] reported on the morphology of the copolymer
with two-amide sequences.
Thermoplastic elastomers are a class of block copolymers
in which periodic crystallizable ‘‘hard’’ segments are
interspersed with ‘‘soft’’ segments, each of the latter
consisting of a long block of non-crystallizing polymer.
The most common choice for the soft segments is a
polyether, formed from three-carbon or four-carbon mono-
mers, these monomers being either diols or cyclic oxides.
Each hard segment is a relatively short length of a polymer
with capability to bond (generally through hydrogen
bonding) with other hard segments. Polyamides are an
obvious candidate. Under stress, the soft segments of the
solid TPE extend greatly but are eventually restrained by the
mutually bonded hard segments. On the release of stress,
the soft segments retreat into their random configuration.
At a sufficiently high temperature the hard segments de-
bond and the polymer becomes a uniform melt, processable
as any other linear polymer.
In particular, the polyether block amides (PEBAs)
constitute an important family of TPEs. Flesher[220]
introduced the PEBAX1 family as Elf Atochem’s offering,
classifying these materials as Engineering Polymers. Yang
and Tsai[221] analyzed PEBAX 3533 and found it to be
composed of poly(lauryl lactam), i.e., PA 12, poly(tetra-
methylene ether) glycol, and adipic acid (to supply required
carboxyl ends). The percentages by weight of the three
components was determined to be 36.3, 60.1, and 3.6,
respectively. Arkema Inc.,[222] now producing the PEBAX
line, advertise it as bridging the gap between thermo-
plastics and rubber. Properties depend on the relative
amounts of polyamide and polyether. Chen[223] evaluated
PEBAX2533 (not 3533) as a polymeric membrane for gas
separation processes. Evonik Industries[224] supplies a
family of VESTAMID1E polyamide 12 elastomers. In a
document by the former supplier Degussa AG,[225] the
benefits of employing a hard segment of polyamide, and in
particular PA 12, are stated as the chemical resistance of
polyamides and the low moisture absorption of PA 12.
Further, on TPEs, a group under the leadership of
Gaymans has explored the effect of polyamide hard
segment length or position, using segments of uniform
length in each evaluation. This work is in the same spirit as
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that of Garg et al.[214] and all of these studies are of interest if
only for the techniques used to generate the oligomers of
uniform lengths. In the first of two studies, van der Schuur
et al.[226] worked with poly(propylene oxide), capped on the
ends with toluene diisocyanate. An amine-ended substance
was then used to join the ends, reacting with the isocyanate
ends to create urea linkages. Three candidates for this
amine-ended substance were tested: HMD by itself, a trimer
consisting of two HMD segments attached to a terephthalic
segment, and a pentamer consisting of three HMD
segments and two terephthalic. These compounds were,
respectively, denoted as ‘‘6,’’ ‘‘6T6,’’ and ‘‘6T6T6.’’ Part of the
van der Schuur arrangement is shown in Formula 17.
Using only ‘‘6’’ (i.e., HMD) produced just urea links, which
were shown not to hydrogen-bond with one another. ‘‘6T6’’
introduced two amide links and ‘‘6T6T6’’ introduced four
amide links, which were shown to form crystalline regions
by bonding with hard segments in other chains. The result
was an increase in modulus and melting temperature and
an improvement in elastic properties, at no cost to favorable
mechanical properties. Arun et al.[227] also used trimers of
HMD and TPA (‘‘T6T’’), this time to join hydroxyl-ended
poly(trimethylene oxide). They varied the number and
position (end-chain, mid-chain) of the hard segments and
studied the effects on crystallinity and mechanical proper-
ties. Finally, Stephen et al.[228] used ‘‘T6T6T’’ to successfully
add a crystallizing component to the amorphous Engineer-
ing Polymer polysulfone. The resulting polymer has high
dimensional and solvent resistance. An important observa-
tion was that the mono-disperse ‘‘T6T6T’’ segments
retained their integrity in spite of high-temperature melt
polymerization with the co-component.
The Hoechst Celanese company have marketed a liquid
crystalline polymer, VectraTMB-950 in which some of the
links are amidic. Kuixiang et al.[229] state a molar
composition for this material of 60% 6-hydroxy-2-
naphthoic acid, 20% TPA, and 20% para-aminophenol. An
objective evaluation of this relatively new PEA was given by
Goodfellow.[230] It is truly thermotropic in the sense that it
can be processed in the melt, requiring no solvent. It is
classed as a self-reinforcing polymer (SRP) because of the
high stiffness and orientation of the molecules. It is forecast
to be useful in ‘‘mechanical and electronic components that
Poly(propylene oxide)
O
O CH CH₂ O CH CH₂ O C N
H CH₃
CH₃ CH₃ Toluene
diisocyanate NH
O O
N (CH₂)₆ N C C N (CH₂)₆ N C O into developing polymers might wisely be redirected into
H H H H
HMD-TPA chain joiner
Formula 17. Amide-based hard segment in a polyether.
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require injection molding to very close tolerances, e.g.,
complex electronic connectors.’’
With its amine ends, a polyamide can provide sites for
acid dyes in a copolymer where the other components are
inert to these dyes. Wang and Hu[231] blended a copolya-
mide with poly(trimethyleneterephthalamide), i.e., (PTT)
polymer, to produce an acid-dyeable fiber. The copolyamide
consisted of HMD and adipic acid and also the trifunctional
diethylenetriamine (DETA). The last provided an extra
amine end beyond that required for polymerization. The
study demonstrated optimum results with weight ratio of
95 to 5 of PTT to copolyamide and with the DETA
constituting 25 mol-% of the copolyamide. The desired
dye uptake was achieved and with little adverse effect on
mechanical and thermal stability. Because the copolyamide
and the PTT are immiscible, a compatibilizer (Surlyn1) was
required.
Reflections
The amide linkage is truly a prodigy among organic
functional groups. It combines covalent strength with a
powerful polarity, producing stable polymer molecules that
adhere to one another and that can often form bodies of
high-melting coherent crystallinity. Many of the polymers
that take advantage of these qualities are made from quite
inexpensive starting materials. It is no surprise that
polyamides have had seventy years of popularity.
New polyamides and copolyamides continue to be
developed. The biggest step so far has been the incorpora-
tion of monomers containing aliphatic and/or aromatic
rings. These structures have helped to keep polyamides in
the midst of the general effort to insert polymers into
applications that currently use metals and ceramics,
applications that generally feature high-temperature
and/or other extreme conditions. Other uses have entirely
different requirements, for which polyamides have also
been tailored, sometimes by actually tempering the very
coherence and stiffness of the base polymer.
While the number of possible monomers is limited (not
least by economics), the number of monomer combinations
is limitless. The search for new copolymer formulations will
continue to be worthwhile both for academics and
industrialists.
Unfortunately, enthusiasm for polymer development is
often dampened by the realization that the cost of novel
monomers precludes commercialization, unless the poly-
mer has properties that are superior and/or unique and that
are highly valued by processors. Some of the effort that goes
developing ways to make cheaper monomers.
Increasing attention is being paid to the source of
monomers. Materials that are derived from vegetable (or
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Polyamides – Still Strong After Seventy Years
animal) matter find favor over those that originate from
fossil sources. Manufacturers are already adding renew-
able-sources–based polymers to their offerings and making
sure that this feature is high-lighted in the labeling of the
product. Thus another area for fruitful development opens
up, identifying biologic sources and defining the processes
for converting these materials into the required monomers.
As the trend to sustainability strengthens, it is possible that
some well-established polymers will be phased out because
there is no bio-sourced monomer.
The seventy years of polyamide success have been
accompanied by eighty years of continuous scientific study.
The work from the early and middle years is full of
information that can be of value to the present-day student
of the polyamides. Among the past investigators there were
at least ‘‘near-giants,’’ on whose shoulders it is beneficial to
stand and on whose work to profit.
Acknowledgements: The author thanks professional colleagues,
including Prof. Kim McAuley of Queen’s University, who reviewed
the paper and made very useful suggestions.
Received: March 16, 2010; Revised: August 13, 2010; Published
online: November 22, 2010; DOI: 10.1002/mren.201000017
Keywords: nylon; polyamides
[1] US Federal Trade Commission, The Textile Fiber Products
Identification Act, 16 CFR Part 303.7.
[2] ASTM International, ‘‘Standard Specification for Polyphtha-
lamide (PPA) Injection Molding Materials’’, D5336-03, 2003.
[3] E. Fukada, IEEE Transact, Dielectr. Electr. Insul. 2006, 13, 1110.
[4] A. Petchsuk, W. Supmak, A. Thanaboonsombut, J. Appl.
Polym. Sci. 2009, 114, 1048.
[5] J. N. Weber, ‘‘Polyamides (General)’’, in: Encyclopedia of
Chemical Technology, 4th edition, J. I. Kroschwitz,
M. Howe-Grant, Eds., J. Wiley & Sons, New York 1996.
[6] J. Zimmerman, ‘‘Polyamides’’, in: Encyclopedia of Polymer
Science and Engineering, 2nd edition, J. I. Kroschwitz, Ed.,
J. Wiley & Sons, New York 1988.
[7] M. I. Kohan, ‘‘Nylon Plastics Handbook’’, Hanser Publishers,
New York 1995.
[8] G. W. Becker, D. Braun, L. Bottenbruch, R. Binsack, ‘‘Kunstst-
off-Handbuch/Polyamide’’, Hanser Publishers, New York
1998.
[9] H. Staudinger, Ber. Deut. Chem. Ges. 1920, 53, 1073.
[10] H. Staudinger, J. Fritschi, J. Helv. Chim. Acta Deut. 1922, 5,
785.
[11] US 2 071 250 (1937), E. I. DuPont de Nemours and Co., Inc.,
inv.: W. H. Carothers.
[12] E. K. Bolton, Ind. Eng. Chem. 1942, 34, 53.
[13] D. A. Hounshell, J. K. Smith, Jr., Invent. Technol. 1988, 4, 40.
[14] W. H. Carothers, G. J. Berchet, J. Am. Chem. Soc. 1930, 52,
5289.
[15] US 2 241 321 (1941), I. G. Farben Industrie AG. inv.:
P. Schlack.
Macromol. React. Eng. 2011, 5, 22–54
www.MaterialsViews.com ß 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.mre-journal.de
[16] P. Matthies, W. F. Seydl, ‘‘History and Development of
Nylon 6’’, in: High Performance Polymers: Their Origin
and Development, R. B. Seymour, G. S. Kirshenbaum, Eds.,
Elsevier, New York 1986.
[17] US 3 063 966 1962, E.I. DuPont de Nemours and Co., Inc.,
invs.: S. L. Kwolek, P. W. Morgan, W. R. Sorenson.
[18] US 3 671 542 (1972), E.I. DuPont de Nemours and Co., Inc.,
inv.: S. L. Kwolek.
[19] US 3 819 587 (1974), E.I. DuPont de Nemours and Co., Inc.,
inv.: S. L. Kwolek.
[20] J. A. Fitzgerald, R. S. Irwin, ‘‘Kevlar1 Aramid Fibers’’, in: High
Value Polymers, A. H. Fawcett, Ed., Royal Society of Chem-
istry, Cambridge 1991.
[21] S. M. Aharoni, ‘‘n-Nylons: Their Synthesis, Structure, and
Properties’’, John Wiley & Sons Ltd, Chichester 1997.
[22] Chemsystems Online. PERP Program – Nylon 6 and Nylon
66, Nexant, Inc., White Plains 2009.
[23] A. Anton, ‘‘Polyamides (Fibers)’’, in: Encyclopedia of Chemi-
cal Technology, 4th edition, J. I. Kroschwitz, M. Howe-Grant,
Eds., J. Wiley & Sons, New York 1996, p. 519.
[24] C. F. Horn, B. T. Freure, H. Vineyard, H. J. Decker, J. Appl.
Polym. Sci. 1963, 7, 887.
[25] M. Ehrenstein, S. Dellsperger, C. Kocher, N. Stutzmann,
C. Weder, P. Smith, Polymer 2000, 41, 3531.
[26] R. Puffr, V. Kubanek, ‘‘Lactam Based Polyamides Polymeri-
zation Structure’’, CRC-Press/Taylor & Francis, London 1991.
[27] T. Yamanobe, Y. Kurihara, H. Uehara, T. Komoto, J. Mol.
Struct. 2007, 829, 80.
[28] C. S. Powell, D. S. Kalika, Polymer 2000, 41, 4651.
[29] N. A. Jones, E. D. T. Atkins, M. J. Hills, Macromolecules 2000,
33, 2642.
[30] S. Moore, Modern Plast. Worldwide 2008, 20.
[31] BASF Engineering Plastics, press release, January 23, 2009.
[32] DSM Stanyl1 website: www.dsm.com/le/en_US/Stanyl/
html/homepage.htm.
[33] DSM Engineering Plastics, press release, November 14,
2007.
[34] R. J. Gaymans, T. E. C. Van Utteren, J. W. A. Van den Berg,
J. Schuyer, J. Polym. Sci., Polym. Chem. Ed. 1977, 15, 537.
[35] J. Heard, C. F. Mascone, Chem. Eng. 1986, 21.
[36] R. J. Gaymans, V. S. Venkatraman, J. Schuijer, J. Polym. Sci.,
Polym. Chem. Ed. 1984, 22, 1373.
[37] C. Koning, L. Teuwen, R. De Jong, G. Janssen, B. Coussens,
High Perform. Polym. 1999, 11, 387.
[38] DSM Engineering Plastics, press release, July 13, 2009.
[39] Modern Plast. Worldwide 2008.
[40] H. J. Nieschlag, J. A. Rothfus, V. E. Sohns, R. B. Perkins, Jr., Ind.
Eng. Chem., Prod. Res. Dev. 1977, 16, 101.
[41] Evonik Industries, product bulletin: ‘‘VESTAMID1Terra’’.
[42] DuPont: product announcement ‘‘Zytel1 Long Chain Poly-
amides’’, 2010.
[43] D. Smock, Design News 2009, http://www.designnews.com.
[44] C. Bennett, E. Kaya, A. M. Sykes, W. L. Jarrett, L. J. Mathias,
J. Polym. Sci., Polym. Chem. Ed. 2009, 47, 4409.
[45] M. Ehrenstein, P. Smith, C. Weder, Macromol. Chem. Phys.
2003, 204, 1599.
[46] H. Mutlu, M. A. R. Meier, Macromol. Chem. Phys. 2009, 210,
1019.
[47] V. Bulacovschi, C. L. Simionescu, J. Macromol. Sci. Chem.
1985, A22, 561.
[48] US 3 692 749 (1972), Scholven-Chemie AG, invs.: K. Schmitt,
F. Gude, S. Brandt.
[49] US 4 293 688 (1981), Phillips Petroleum Co., invs.: R. W.
Campbell, W. H. Hill, Jr.
51

www.mre-journal.de
[50] WO 2002/048239 (2002), Asahi Kasei Kabushiki Kaisha
invs.: M. Aramaki, T. Maekawa.
[51] C. Glidewell, G. Ferguson, Acta Cryst. 1996, C52, 1466.
[52] DuPont Aramid Intermediates: Product announcement ‘‘1,4-
Diaminocyclohexane (1,4-DCH)’’, 2008.
[53] Mitsubishi Gas Chemical America, Inc.: Product announce-
ment ‘‘1,3-BAC Highly Reactive Cycloaliphatic Diamine’’.
[54] K. Inoue, S. Hoshino, J. Polym. Sci. : Polym. Phys. Ed. 1980, 18,
697.
[55] M. Endo, Y. Morishima, S. Yano, K. Tadano, Y. Murata,
K. Tsunashima, J. Appl. Polym. Sci. 2006, 101, 3971.
[56] A. Bell, J. G. Smith, C. J. Kibler, J. Polym. Sci., Polym. Chem. Ed.
1965, 3, 19.
[57] US 4 086 276 (1978), Suntech, Inc., invs.: W. A. Butte, Jr.
[58] US 3 012 994 (1961), Eastman Kodak Co., invs.: A. Bell, J. G.
Smith, C. J. Kibler.
[59] US 3 950 310 (1976), Exxon Research and Engineering Co.,
invs.: C. J. Bouboulis.
[60] J. S. Ridgway, J. Polym. Sci.: Polym. Chem. 1974, 12, 2005.
[61] Evonik Industries, Product announcement: ‘‘Trogamid1CX-
Polyamide PA PACM 12’’.
[62] Y. Yang, G. Thompson, J. Song, A. Hiltner, E. Baer, J. Appl.
Polym. Sci. 2009, 112, 163.
[63] EP 1369447 (2003), EMS Chemie AG, inv.: F. S. R. Buehler.
[64] US 2008 002 1143 (2008), invs.: H. Thullen, C. Rytka, F.-S.
Buehler, R. Hala.
[65] US 2008 013 5720 (2008), invs.: F. S. Buhler, C. Rytka.
[66] US 4 205 159 (1980), Bayer AG, invs.: R.-V. Meyer, R. Dhein,
F. Fahnier.
[67] US 3 869 400 (1975), E.I. DuPont de Nemours and Company.
[68] US 3 691 749 (1972), E.I. DuPont de Nemours and Company.
[69] WO 2007/096326 (2007), Arkema, invs.: P. Blondel,
T. Montanari.
[70] F. R. Prince, E. M. Pearce, Macromolecules 1971, 4, 347.
[71] H. W. Hill, Jr., R. W. Campbell, R. S. Shue, Pol. Eng. Sci. 1978, 18,
36.
[72] I. Arvanitoyannis, E. Nikolaou, N. Yamamoto, Angew. Mak-
romol. Chem. 1994, 221, 67.
[73] I. Arvanitoyannis, E. Nikolaou, N. Yamamoto, Macromol.
Chem. Phys. 1995, 196, 1129.
[74] E. Vinken, A. E. Terry, S. Hoffmann, B. Vanhaecht, C. E.
Koning, S. Rastogi, Macromolecules 2006, 39, 2546.
[75] M. Katz, J. Polym. Sci. 1959, 40, 337.
[76] K. Saotome, H. Komoto, J. Polym. Sci. A-1 1966, 4, 1463.
[77] W.-Z. Wang, Y.-H. Zhang, Polym. Lett. 2009, 3, 470.
[78] Mitsubishi Gas Chemical Company, document ‘‘MGC-A
History of Nylon-MXD6’’, 2009 April 9.
[79] B. S. Sprague, R. W. Singleton, Text. Res. J. 1965, 35, 999.
[80] T. I. Shein, G. I. Kudryavtsev, R. P. Biber, G. P. Lyubimtseva,
Fibre Chem. 1971, 1, 683.
[81] D. C. Vogelsong, J. Polym. Sci. 1962, 57, 895.
[82] R. D. Chapman, D. A. Holmer, O. A. Pickett, K. R. Lea, J. H.
Saunders, Text. Res. J. 1981, 51, 564.
[83] D. Glasscock, W. Atolino, G. Kozielski, M. Martens, ‘High
Performance Polyamides Fulfill Demanding Requirements for
Automotive Thermal Management Components’’, Dupont,
2008.
[84] J. B. Jackson, Polymer 1969, 10, 159.
[85] W. Nielinger, B. Brassat, D. Neuray, Angew. Makromol. 1981,
98, 225.
[86] US 2009 010 5412 (2009), E.I. DuPont de Nemours & Co. invs.
M. M. Martins, A. T. Mutel,
[87] P. W. Morgan, S. L. Kwolek, Macromolecules 1975, 8, 104.
Macromol. React. Eng. 2011, 5, 22–54
52
ß 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
K. Marchildon
[88] US 4 042 571 1977, Teijin Ltd. invs.: S. Kawase, T. Shima,
K. Moriyama.
[89] S. Yang, P. Fu, M. Liu, Y. Wang, Q. Zhao, J. Appl. Polym. Sci.
2010, 118, 1094.
[90] V. E. Shashoua, W. M. Eareckson III, J. Polym. Sci. 1959, 50,
343.
[91] W.-Z. Wang, Y.-H. Zhang, Express Polym. Lett. 2009, 3, 470.
[92] W. Wang, X. Wang, R. Li, B. Liu, E. Wang, Y. Zhang, J. Appl.
Polym. Sci. 2009, 114, 2036.
[93] Prochase Enterprise Co. Ltd, Product bulletin ‘‘Polyamide
9T’’, January 15, 2009.
[94] T. F. Novitsky, C. A. Lange, L. J. Mathias, S. Osborn, R. Ayotte,
Polymer 2010, 51, 2417.
[95] US 7 009 029 (2006), Kuraray Co., Ltd., invs.: H. Oka,
H. Matsuoka, T. Kuki.
[96] M. Kaiser, Kunstst. Int. 2008, 111.
[97] H. Liu, G. Yang, A. He, M. Wu, J. Appl. Polym. Sci. 2004, 94, 819.
[98] R. G. Quynn, Text. Res. J. 1970, 40, 677.
[99] B. S. Gorton, J. Appl. Polym. Sci. 1965, 9, 3753.
[100] DSM Engineering Plastics, press release, February 10, 2009.
[101] US 6747120 (2004), DSM IP Assets B.V., invs.: R. Rulkens, R. C.
B. Crombach.
[102] L. Zielezinski, ‘‘High-performance Thermoplastics for Sensors
and Actuators Under the Hood’’, DuPont de Nemours, 2007.
[103] US 4 603 166 (1986), Amoco Corporation, invs.: Y.-T. Chen,
L. W. Autry, J. A. Richardson, D. P. Sinclair.
[104] US 2010 006 3245 (2010), DSM IP Assets B.V., inv.: R. Rulkens,
[105] US 5 585 429 (1996), Amoco Corporation, inv.: M. G. Reich-
mann.
[106] US 3 049 518 (1962), E.I. DuPont de Nemours & Co., Inc., inv.:
C. W. Stephens.
[107] US 3 079 219 (1963), E.I. DuPont de Nemours & Co., Inc., inv.:
F. W. King.
[108] L. K. McCune, Text. Res. J. 1962, 32, 762.
[109] C.-P. Yang, S.-H. Hsiao, Y.-S. Lin, J. Appl. Polym. Sci. 1994, 51,
2063.
[110] S. Mehdipour-Ataei, Y. Sarrafi, M. Hatami, Eur. Polym. J.
2005, 41, 2887.
[111] M. A. Rabjohns, P. Hodge, P. A. Lovell, Polymer 1997, 38, 3395.
[112] J. Preston, ‘‘Polyamides, Aromatic’’, in: Encyclopedia of Poly-
mer Science and Engineering, Vol. 11, 2nd edition, J. I. Krosch-
witz, Ed., J. Wiley & Sons, New York 1988, p. 381.
[113] J. Gallini, ‘‘Polyamides, Aromatic’’, in: Encyclopedia of Poly-
mer Science and Engineering, 3rd edition, J. I. Kroschwitz, Ed.,
J. Wiley & Sons, New York 2005.
[114] J. M. Garcia, F. C. Garcia, F. Serna, J. L. de la Pena, Prog. Polym.
Sci. 2010, 35, 623.
[115] R. E. Wilfong, J. Zimmerman, J. Appl. Polym. Sci. 1973, 17,
2039.
[116] K. H. Gardner, A. D. English, V. T. Forsyth, Macromolecules
2004, 37, 9654.
[117] M. Fukuda, H. Kawai, J. Polym. Sci., Polym. Phys. Ed. 1997, 35,
1423.
[118] DuPont announcement, Daily News Record 1987, (March).
[119] M. G. Dobb, R. M. Robson, J. Mater. Sci. 1990, 25, 459.
[120] Y. Rao, A. J. Waddon, R. J. Faris, Polymer 2001, 42, 5925.
[121] Y. Rao, A. J. Waddon, R. J. Faris, Polymer 2001, 42, 5937.
[122] J. G. Cook, ‘‘Handbook of Textile Fibres, II. Man-Made Fibres’’,
4th edition, Textile Book Service, Metuchen 1968.
[123] ‘‘Moisture Effects and Processing Information for NOMEX1
Paper’’, DuPont bulletin, 2002.
[124] M. Shubha, H. V. Parimala, K. Vijayan, J. Mater. Sci. Lett. 1993,
12, 60.
www.MaterialsViews.com
Polyamides – Still Strong After Seventy Years
[125] J. J. Ferreiro, J. G. De La Campa, A. E. Lozano, J. D. Abajo,
J. Polym. Sci., Polym. Chem. Ed. 2005, 43, 5300.
[126] A. K. Chaudhuri, B. Y. Min, E. M. Pearce, J. Polym. Sci., Polym.
Chem. Ed. 1980, 18, 2949.
[127] Evonik Industries, product bulletin: ‘‘VESTAMIN1 TMD’’.
[128] Degussa, product bulletin: ‘‘TROGAMID1 Transparent poly-
amides with an outstanding cobination of properties’’.
[129] US 4 476 280 (1984), Standard Oil Co., invs.: W. Poppe, Y.-T.
Chen.
[130] US 4 495 328 (1985), Standard Oil Co., invs.: W. Poppe, Y.-T.
Chen, L. W. Autry.
[131] US 2 752 328 (1956), E.I. DuPont de Nemours & Co., inv.: E. E.
Magat.
[132] INVISTA, product bulletin: ‘‘Dytek1 A’’, 2005.
[133] J. D. Menczel, M. Jaffe, C. K. Saw, T. P. Bruno, J. Therm. Anal.
1996, 46, 753.
[134] P. Villasenor, L. Franco, J. Puiggali, Polymer 1999, 40, 6887.
[135] J. M. Stouffer, H. W. Starkweather, Jr., B. S. Hsiao, P. Avakian,
G. A. Jones, Polymer 1996, 37, 1217.
[136] M. Y. Keating, K. H. Gardner, H. Ng, D. N. Marks, W. S. Yung,
P. Avakian, H. W. Starkweather, Jr., J. Therm. Anal. Cal. 1999,
56, 1133.
[137] H. W. Starkweather, Jr., P. Avakian, K. H. Gardner, B. S. Hsiao,
M. Y. Keating, H. Ng, J. Therm. Anal. Cal. 2000, 59, 519.
[138] US 5 378 800 1995, E.I. DuPont de Nemours & Co., DuPont
Canada Inc., invs.: S. I. Mok, R. U. Pagilagan.
[139] INVISTA, product bulletin: ‘‘DYTEK1 EP (1,3-Pentanedia-
mine, DAMP’’, 2005.
[140] US 3 846 507 (1974), Union Carbide Canada Limited, invs.:
E. C. Thomm, B. R. Knowlton.
[141] US 3 184 436 (1965), E.I. DuPont de Nemours & Co., inv.: E. E.
Magat.
[142] A. Gomez-Valdemoro, V. Calderon, N. San-Jose, F. C. Garcia,
J. L. de la Pensa, J. M. Garcia, J. Polym. Sci. A: Polym. Chem.
2009, 47, 670.
[143] US 2 430 860 (1947), E.I. DuPont de Nemours & Co., inv.:
T. Le Sueur Cairns.
[144] C. Sease, Stud. Conserv. 1981, 26, 102.
[145] US 2 430 907 1947, E.I. DuPont de Nemours & Co., inv.:
T. Le Sueur Cairns.
[146] US 5 411 663 (1995), Micron Separations, Inc., invs: J. S.
Johnson.
[147] US 3 363 025 (1968), Continental Can Company, Inc., C. W.
Fitko, A. Ravve.
[148] H. C. Haas, S. G. Cohen, A. C. Oglesby, E. R. Karlin, J. Polym. Sci.
1955, 15, 427.
[149] M. A. Schaffer, E. K. Marchildon, K. B. McAuley, M. F. Cun-
ningham, J. Macromol. Sci. Rev. Macromol. Chem. Phys. 2000,
C40, 233.
[150] US 3 687 904 (1972), Imperial Chemical Industries Ltd.
[151] US 4 596 742 (1986), Monsanto, invs.: D. Selivansky, J. H.
Southern.
[152] US 2 863 857 (1958), Imperial Chemical Industries Ltd, invs.:
W. Costain, N. Fletcher, B. J. Habgood.
[153] T. Kiyotsukuri, M. Murata, M. Sugimoto, N. Tsutsumi, Polym.
Int. 1994, 34, 173.
[154] L. Dai, N. Huang, Z. Tang, K.-D. Hungenberg, J. Appl. Polym.
Sci. 2001, 82, 3184.
[155] US 6 835 799 2004, DSM IP Assets B.V. invs.: A. J. Nijenhuis,
R. Aberson, B. J. R. Scholtens.
[156] WO 2001/053382 (2001), US 6 504 004 (2002), E.I. duPont de
Nemours & Co., G. E. Zahr.
[157] U. Stier, M. Schweizer, J. Appl. Polym. Sci. 2007, 106, 425.
Macromol. React. Eng. 2011, 5, 22–54
www.MaterialsViews.com ß 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.mre-journal.de
[158] US 7 005 097 (2006), Boston Scientific Scimed, Inc., invs.:
L. Wang, J. S. Lindquist, N. Lee.
[159] Bruggemann Chemical, product bulletin: ‘‘BRUGGOLEL1M
1251 Chain Extender for Polyamides’’.
[160] DSM, product bulletin: ‘‘Chain extension: ALLINCO1 linear
chain extender for polyesters and nylons’’.
[161] US 6 228 980 (2001), DSM N.V., invs.: J. A. Loontjens, B. J. M.
Plum.
[162] C. Lu, T. Chen, X. Zhao, X. Ren, X. Cai, J. Polym. Sci. B: Polym.
Phys. 2007, 45, 1976.
[163] J. H. Hong, C. W. Choi, S. Ramasundaram, A. A. Prabu, J. S. Lee,
K. J. Kim, J. H. Yang, D. J. Lee, Polym. Degrad. Stab. 2008, 93,
392.
[164] C. Lu, L. Chen, R. Ye, X. Cai, J. Macromol. Sci. B: Phys. 2008, 47,
986.
[165] M. Acevedo, A. Fradet, J. Polym. Sci. A: Polym. Chem. 1993, 31,
1579.
[166] J. F. Kenney, Polym. Eng. Sci. 1968, 8, 216.
[167] S. J. Allen, J. Text. Inst. Proc. 1953, 44, 8.
[168] US 2 193 529 (1940), E.I. DuPont de Nemours & Co., invs.:
D. D. Coffman.
[169] E. D. Harvey, F. J. Hybart, J. Appl. Polym. Sci. 1970, 14, 2133.
[170] K. Suehiro, T. Egashira, K. Imamura, Y. Nagano, Acta Polym.
1989, 40, 4.
[171] M. Zilberman, A. Siegmann, M. Narkis, J. Macromol. Sci. Phys.
1996, B35, 1.
[172] C. G. Johnson, C. C. Cypcar, L. J. Mathias, Macromolecules
1995, 28, 8535.
[173] D. P. Garner, P. D. Fasulo, J. Appl. Polym. Sci. 1988, 36, 495.
[174] I. Goodman, A. H. Kehayoglou, Eur. Polym. J. 1983, 19,
321.
[175] A. H. Kehayoglou, I. Arvanitoyannis, Eur. Polym. J. 1990, 26,
261.
[176] A. H. Kehayoglou, I. Arvanitoyannis, Polymer 1992, 33, 4095.
[177] P. J. Flory, J. Chem. Phys. 1947, 15, 684; 1949, 17, 223.
[178] P. J. Flory, ‘‘Principles of Polymer Chemistry’’, Cornell Uni-
versity Press, Ithica 1953, p. 70.
[179] H. W. Starkweather, Jr., P. Zoller, G. A. Jones, J. Polym. Sci.,
Polym. Phys. Ed. 1984, 22, 1615.
[180] MatWeb, Material Property Data bulletin: ‘‘DuPont Selar1
PA 3426 Nylon Barrier Resin’’, 2009.
[181] O. B. Edgar, R. Hill, J. Polym. Sci. 1952, 8, 1.
[182] A. J. Yu, R. D. Evans, J. Polym. Sci. 1960, 42, 249.
[183] M. Levine, S. C. Temin, J. Polym. Sci. 1961, 59, 241.
[184] WO 1997/043330 (1997), US 5 981 692 (1999), DuPont
Canada Inc., inv.: C. Leboeuf.
[185] US 5 739 262 (1998), Bayer AG, invs.: H. Morhenn,
D. Brokmeier, W. Nielinger,
[186] Y. Men, J. Rieger, Eur. Polym. J. 2004, 40, 2629.
[187] W. H. Jo, D. H. Baik, J. Polym. Sci., Polym. Phys. Ed. 1989, 27,
673.
[188] D. Y. Baik, W. H. Jo, J. Polym. Sci., Polym. Phys. Ed. 1990, 28,
595.
[189] W. H. Jo, J. H. Kim, D. H. Baik, Polymer (Korea) 1987, 11, 64.
[190] P. Scarfato, L. Di Maio, L. Incarnato, D. Acierno, A. Mariano,
Packag. Technol. Sci. 2002, 15, 9.
[191] G. Rusa, E. Rusa, High Perform. Polym. 2004, 16, 569.
[192] US 5 321 068 (1994), E.I. DuPont de Nemours & Co., invs.:
M. R. De Witt, Jr.
[193] US 5 110 900 (1992), E.I. DuPont de Nemours & Co., invs.: J. A.
Hammond, Jr., D. N. Marks.
[194] US 5 162 491 (1992), E.I. DuPont de Nemours & Co., invs.: J. A.
Hammond, Jr., D. N. Marks.
53

www.mre-journal.de
[195] US 5 185 428 (1993), E.I. DuPont de Nemours & Co., invs.: J. A.
Hammond, Jr., D. N. Marks.
[196] US 4 559 196 (1985), E.I. DuPont de Nemours & Co., invs.:
H. Kobsa, W. T. Windley.
[197] K. Kudo, T. Seguie, M. Hirami, J. Appl. Polym. Sci. 1992, 44,
1625.
[198] X. Zhang, T. Xie, G. Yang, Polymer 2006, 47, 2116.
[199] R. W. Johnson, J. M. Valdespino, R. L. Gordon, G. E. Miller,
R. W. Kight, ‘‘Polyamides from Fatty Acids’’, in: Encyclopedia
of Polymer Science and Engineering, 2nd edition, J. I. Krosch-
witz, Ed., J. Wiley & Sons, New York 1988.
[200] US 3 960 984 (1976), E.I. DuPont de Nemours & Co., inv.: M. I.
Kohan.
[201] US 2 285 009 (1942), E.I. DuPont de Nemours & Co., invs.:
M. M. Brubaker, W. E. Hanford, R. H. Wiley.
[202] P. Larose, Can. J. Chem. 1957, 35, 1230.
[203] H. C. Beachell, D. W. Carlson, J. Polym. Sci. 1959, 40, 543.
[204] N. S. Baer, N. Indictor, A. Joel, Restaurator 1978, 2, 5.
[205] W. H. Phelan, N. S. Baer, N. Indictor, Bulletin of the American
Group, International Institute for Conservation of Historical
and Artistic Works, 1971, 11C-AG-1971.
[206] C. R. Davis, J. Appl. Polym. Sci. 1996, 62, 2237.
[207] US 4 102 871 (1978), BASF AG, invs.: P. Horn, H-d. Haertl,
K. H. Illers.
[208] X. Chen, H. Zhong, L. Jia, J. Ning, R. Tang, J. Qiao, Z. Zhang, Int.
J. Adhes. Adhes. 2002, 22, 75.
[209] US 3 883 487 (1975), Plate GmbH, invs.: F. Raabe, E. De Jong.
[210] US 6 590 063 (2003), EMS-Chemie AG, invs.: G. Poessnecker,
J. Spindler, E. Kinkelin.
[211] V. I. Besshaposhnikova, S. E. Artemenko, I. G. Polushenko,
Fibre Chem. 2004, 36, 59.
[212] US 2007 010 4971 (2007), DEGUSSA AG, invs.: R. Wursche,
F.-E. Baumann, B. Kuting, M. Wielputz, P. Kreidler, H. Hager.
[213] US 2008 011 9632 (2008), DEGUSSA GmbH, invs.:
F.-E. Baumann, R. Wursche, H. Hager, S. Bollmann, K. Alting.
Macromol. React. Eng. 2011, 5, 22–54
54
ß 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
K. Marchildon
[214] P. Garg, H. Keul, D. Klee, M. Moller, Macromol. Chem. Phys.
2009, 210, 1754.
[215] S. Wiegand, M. Steffen, R. Steger, R. Koch, J. Polym. Environ.
1999, 7, 145.
[216] T. Ferre, L. Franco, A. Rodriguez-Galan, J. Puiggali, Polymer
2003, 44, 6139.
[217] K. Hemmrich, M. Meersch, U. Wiesemann, J. Salber, D. Klee,
Th. Gries. N. Pallua, Tissue Eng. 2006, 12, 3557.
[218] I. Bechthold, K. Bretz, S. Kabasci, R. Kopitzky, A. Springer,
Chem. Eng. Technol. 2008, 31, 647.
[219] P. Garg, P. Lohakare, P. Mela, M. Moller, B. Blumich,
A. Adams, Macromol. Chem. Phys. 2010, 211, 471.
[220] J.R. Flesher, Jr., ‘‘PEBAX1 Polyether Block Amide – A New
Family of Engineering Thermoplastic Elastomers’’, in:
‘‘High Performance Polymers: Their Origin and Develop-
ment’’, R. B. Seymour, G. S. Kirshenbaum, Eds. Elsevier,
New York 1986.
[221] I.-K. Yang, P.-H. Tsai, Polym. Eng. Sci. 2007, 47, 235.
[222] Arkema product bulletin: ‘‘pebax’’, 2006.
[223] J. C.-Y. Chen, Master Thesis, University of Waterloo 2002.
[224] Evonik Industries, product bulletin: ‘‘VESTAMID1 E–Poly-
amide 12 Elastomers’’.
[225] Degussa product bulletin: ‘‘High performance Polymers –
Polyamide 12 Elastomers’’.
[226] M. van der Schuur, B. Noordover, R. J. Gaymans, Polymer
2006, 47, 1091.
[227] A. Arun, K. Dullaert, R. J. Gaymans, Macromol. Chem. Phys.
2009, 210, 48.
[228] R. Stephen, C. M. Gibon, M. Weber, R. J. Gaymans, J. Polym.
Sci., Polym. Chem. Ed. 2009, 48, 63.
[229] M. Kuixiang, T.-S. Chung, R. J. Good, J. Polym. Sci., Polym.
Phys. Ed. 1998, 36, 2337.
[230] ‘Goodfellow’ product descriptor: ‘‘Vectra B–Liquid Crystal
Polyester/Amide Copolymer’’, June 26, 2003.
[231] L.-J. Wang, Z.-H. Hu, Text. Res. J. 2009, 79, 1135.
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