190 Recent Patents on Materials Science 2009, 2, 190-208

Recent Patents on Aromatic Polyamides

Miriam Trigo-López, Pedro Estévez, Noelia San-José, Ana Gómez-Valdemoro, Félix C. García,
Felipe Serna, José L. de la Peña and José M. García*

Departamento de Química, Facultad de Ciencias, Universidad de Burgos, Plaza de Misael Banuelos s/n, 09001 Burgos,
Spain

Received: February 28, 2008; Accepted: June 3, 2009; Revised: June 8, 2009
Abstract: Aromatic polyamides are high performance materials with superior thermal and mechanical properties which
make them extremely useful for advanced technologies. These polymers can be transformed into high-tensile strength
synthetic fibers and into flame and cut-resistant materials that have technological applications in the field of coatings and
fillers in the aerospace and armaments industry, in asbestos substitutes, electrical insulation, bullet-proof body armor,
industrial filters, and sports fabrics, among others. This article sets out to review the existing literature and recent patent
claims that describe the design, the preparation and the applications of wholly aromatic polyamides, semiaromatic
polyamides and poly(amide imide)s.
Keywords: Aramids, aromatic polyamides, phthalamides, semiaromatic polyamides, poly(amide imide)s, high performance
polymers, applications.

INTRODUCTION research is being conducted to enhance their processability

Research and development in the field of materials
science and technology are directed toward the preparation
of new materials capable of overcoming specific problems,
and improving, or reducing the cost of present-day industrial
processes. In this regard, if Science may be considered
essential for the welfare of humankind, then materials
science clearly contributes to ongoing social and economic
progress.
In contrast to conventional polymeric materials, high-
performance materials are characterized by specific criteria,
such as higher thermal resistance, higher mechanical
strength, lower specific densities, higher conductivity, higher
thermal, electrical or sound insulation properties, superior
flame resistance, etc [1].
Aromatic polyamides are high performance materials
with superior thermal and mechanical properties which make
them useful for advanced technologies. The better-known
commercial aramides -the shortened form of aromatic
polyamides- are poly(p-phenylene terephthalamide) (PPPT)
and poly(m-phenylene isophthalamide) (PMPI). Both of
these polymers can be transformed into flame, cut-resistant
and high-tensile strength synthetic fibers, with technological
applications in the field of coatings and fillers in the
aerospace and armaments industry, in asbestos substitutes,
electrical insulation, bullet-proof body armor, industrial
filters, and sport fabrics, among others. However, their
extremely high transition temperatures, which lie above their
decomposition temperatures, and poor solubility in common
organic solvents give rise to processing difficulties and limit
their applications. As a consequence, basic and applied
and solubility, in order to broaden the scope of their techno-
logical applications.
This article sets out to review the existing literature and
recent patent claims that describe the design, the preparation
and the applications of wholly aromatic polyamides, semi-
aromatic polyamides and poly(amide imide)s.
STATE OF THE ART
In the field of materials science, a gap often exists
between basic and applied research and development. The
former is disseminated throughout the world by researchers
publishing in scientific journals, and the latter is more often
subjected to some sort of intellectual protection, the most
common being the patent.
Nowadays, basic research is carried forward in two ways:
a) by attempting to overcome the problems that are asso-
ciated with the high cohesive energy of aromatic polyamides,
which give rise to intractable materials due to their extremely
low solubility and exceptionally high thermal transition
temperatures; and, b) by expanding the scope of their
applications as high performance materials to new and
promising areas of materials research, such as active optics,
luminescence, ionic exchange, flame resistance, and fiber
forming materials, all of which hold the promise of interes-
ting results in fast-evolving areas of research.
This review examines the descriptions of industrial
applications that are currently patented. Most of the patents
are based on commercial materials, and a few describe the
design and synthesis of novel polyamide chemical structures
for specific applications or with specific characteristics.

*Address correspondence to this author at the Departamento de Química,

Facultad de Ciencias, Universidad de Burgos. Plaza de Misael Banuelos s/n,
09001 Burgos, Spain; Tel: +34 947 258 085; Fax: +34 947 258 831;
E-mail: jmiguel@ubu.es
Commercial Polyphthalamides, Poly(Amide Imide)s and
Wholly Aromatic Polyamides
According to the US Federal Trade Commission (FCT),
wholly aromatic polyamides (aramids) are synthetic poly-

1874-4648/09 $100.00+.00 © 2009 Bentham Science Publishers Ltd.

Recent Patents on Aromatic Polyamides
amides in which at least 85% of amide groups are bound
directly to two aromatic rings [2]. Scheme (1) shows the first
commercialized aramids, which are the most important from
an economic point of view, their constituent monomers, and
some of the tradenames they have used over the last 40
years.
The first all-para oriented aramid, poly(p-benzamide)
(PPBA) was marketed by Du Pont under the ‘Fiber B’
tradename. Production only lasted a few years, probably due
to economic reasons. The amino group of the AB monomer
had to be masked as its hydrochloric acid salt to prevent
polymerization. Moreover, the salt is moisture sensitive and
unstable to both light and heat [3]. The polymer was pre-
pared using polar aprotic solvents by a low-temperature
solution method, which yielded a fairly insoluble, stiff,
semicrystalline polymer, soluble only in polar aprotic
solvents with inorganic salts that acted as solubility pro-
moters. In dimethylacetamide (DMA) and N-methyl-
pyrrolidone (NMP) the polymer/solvent system exhibited
lyotropic behavior, and films could be cast, and fibers could
be spun, from the solution [1, 4, 5].
PPBA was replaced on the market by PPPT in 1970
under the tradename of ‘Kevlar®’. Polycondensation was
performed at low temperature in a solution of terephthaloyl
dichloride and p-phenylenediamine in hexamethyl-
phosphoramide (HMPA). Subsequently, a mixture of HMPA
and NMP (2:1) produced a polymer of higher molecular
weight. As HMPA is now understood to be carcinogenic, the
solvent was successfully replaced by a NMP/CaCl2 system
(Azko patent [6]). PPPT is even more insoluble than PPBA
and has to be transformed into fibers by spinning from
lyotropic solutions in concentrated sulfuric acid at high
ClOC COCl
Aromatic
diacid
dichlorides:
isophthaloyl dichloride
H2N NH2
Aromatic
diamines:
m-phenylenediamine
O O
Aramids: N N
H H
poly(m-phenylene isophthalamide) (PMPI)
Tradenames: Nomex®, Phenylon®, Conex®,
Teijinconex®, KM-21®, Durette®, Apyeil®
Scheme 1. Tradenames and chemical structures of diacids and diamines in commercial meta and para-aramids.
Recent Patents on Materials Science 2009, Vol. 2, No. 3 191
temperature (polymer concentration approximately 20%,
temperature: 70-100ºC) [1, 4, 5].
The high-performance properties of the PPPT are a
consequence of its chemical structure. The wholly aromatic
structure with all-para substitutions gives rise to stiff rod-
like macromolecules, having a high cohesive energy and a
high crystallization tendency due to highly favorable
intramolecular hydrogen bonds [7-10]. PPPT fibers can be
transformed into materials and composite materials with
superior thermal and mechanical resistance.
Taking this into account, a wholly aromatic polyamide
with all-meta orientation of the phenylene ring, such as
poly(m-phenylene isophthalamide) (PMPI), produces a less-
linear structure with a concomitant reduction in its cohesive
energy and in its crystallization tendency. Thus, PMPI is a
high-performance polymer, with high thermal and mecha-
nical resistance that is an alternative to PPPT which only
slightly underperforms its rival. It was first described by Du
Pont in 1961 and commercialized in 1967, under the trade-
mark ‘Nomex®’ [11]. Du Pont [12] describes Nomex® as an
“inherently flame-resistant, high-temperature fiber that will
not melt, drip or support combustion in air. It also delivers
outstanding resistance to a broad range of chemicals and is
offered in paper, felt, fabric and fiber forms”.
As a general rule, the aramids cannot be prepared by melt
polycondensation and they are commercially synthesized
with low-temperature polycondensation methods, such as the
Schotten-Baunmann reaction of acid chlorides and amines.
Gaymans [4] and Fink [1] have recently summarized other
reaction methods for these kinds of aramides. Thus, wholly
and partially aromatic polyamides can also be prepared by
reaction of diacids with diisocyanates; by direct polycon-
ClOC COCl
terphthaloyl dichloride
H2N NH2
p-phenylenediamine
O
H
O N N
H
poly(p-phenylene terephthalamide) (PPPT)
Tradenames: Kevlar®, Twaron®, Technora®,
Vniivlon®, Arenka®.
192 Recent Patents on Materials Science 2009, Vol. 2, No. 3 García et al.

densation of diacids and diamines by high temperature
solution methods (phosphorylation method); by direct
polycondensation using thionyl chloride as the activating
agent; by condensation of diacids with the formamidinium
salts of aromatic diamines; by using diamines or acid-amines
and CS2 ; by the reaction of aromatic diacid phenyl esters
with amines; by reaction of diacid halides and activated
diamines through in situ silylation; by assisted microwave
polymerization; etc.
The poly(amide imide)s (PAIs) are also described in this
review, as the aromatic amide group is considered a basic
function of the wholly aromatic polyamides. These high-
performance polymers, the average properties of which lie
somewhere in-between aromatic polyimides and aromatic
polyamides, have been used in industry since the late 1960s.
PAIs are easier to prepare and to process than aramids
and polyimides, as they are less prone to crystallization, and
have lower transition temperatures. These commercial
polymers can be transformed by conventional extrusion and
injection molding, and thermosetting types are also of
commercial importance. Classically, the polymers can be
prepared by reacting equimolecular amounts of trimellitic
acid halide anhydride and a diamine, or by condensation of
aromatic diisocyanate with aromatic tricarboxilic acid
anhydride [13]. Other polymerization methods are: direct
condensation of the aromatic tricarboxylic acid anhydrides
with aromatic diamines; assisted microwave polymerization
etc. [14] Common diamines and diisocyanates monomers are
summarized in Scheme (2), along with the trimellitic
anhydride structure, which is the sole diacid anhydride of
significant commercial importance.
Partially aromatic polyamides, or semiaromatic poly-
amides, polymers in which at least 50% of their constituting
diacids or diamines are aromatic, are also included in this
review. Certain partially aromatic polyamides of some com-
mercial importance are the poly(phthalamide)s, polyamides
in which 60% of the diacid moieties are constituted at least
by the terephthalic and the isophthalic aromatic acids (TPA
and IPA, respectively), which are the most important from a
commercial viewpoint [15]. Some of these polymers are
considered high-performance materials. Their properties are
somewhat lower than those of the wholly aromatic
polyamides, the average properties of which lie in-between
aliphatic polyamides (nylons) and aramids, but they are
easier to prepare and to transform from an industrial
perspective. The nomenclature of some of the common
semiaromatic, or aliphatic aromatic polyamides resembles
that used for nylons: the number refers to the chain length on
the diamine followed by the initial of the diacid: I is used for
IPA, T for TPA, and PA for polyamide, Scheme (3). Semi-
aromatic polyamides are usually blended or copolymerized
with aromatic polyamides, with other polyphthalamides,
with amorphous aromatic polyamides or with semiaromatic
polyamides containing nonsimetric monomers, in order to
achieve the required characteristics (moldability, crystalline

O O
HOOC ClOC
Anhydride O O
derivatives:

O O
trimellitic acid anhydride trimellitic acid chloride

H 2N NH2 H2N NH2 H2N NH2

Aromatic
diamines:
(H2N R NH2) O

m-phenylenediamine 4,4'-diaminodiphenyl methane 4,4'-diaminodiphenyl ether

OCN NCO
Disocyanate:
(OCN R NCO)

4,4'-diisocyanatediphenyl methane

O O O
XOC
Polymerization: O + Y R Y X= OH, Y= NCO or N R N
X= Cl, Y= NH2

O O
poly(amide imide)
Poly(amide imide) tradenames: AI polymer®, Pyropel®, Sintimid®, Torlon®, Vylomax®

Scheme 2. Constituting acid anhydride derivatives, diamines and diisocyanate in commercial PAIs.
Recent Patents on Aromatic Polyamides Recent Patents on Materials Science 2009, Vol. 2, No. 3 193

CO CONH CH2 NH
CO CONH CH2 NH n
n

n = 6: PA 6T, ultramid® n = 6: PA 6I
n = 10: PA 10T n = 10: PA 10I

Scheme 3. Chemical structure of common semicrystalline, semiaromatic poly(isophthalamide)s and poly(terephthalamide)s.

degree or amorphous state, transition temperatures, etc.). As

an example, Scheme (4) shows the chemical structure of an
amorphous polyamide.
O O NH
NH
C C
NH
HN
PA 6-3T, Trogamid®
Scheme 4. Chemical structure of commercial amorphous, partially
aromatic poly(terephthalamide)s.
To conclude this section, Table 1 depicts some of the
characteristics of commercial polyamides that have been
considered in the preceding paragraphs.
RECENT AROMATIC POLYAMIDE PATENTS
In this section, we describe recent developments with an
industrial application, including the description of novel
polyamides and their possible applications, which are extrac-
ted from patent claims that have been approved over the last
ten years. The patents have been categorized into ten
sections, although most of the products they describe could
be classified in more than a category. The categories are:
safety and resistant materials; membranes; biomaterials and
polyamide systems for medical applications; optical devices;
electric and electronic devices; architecture materials; pac-
kage materials, filters, gas barrier films and coatings; fibers,
resins and films with diverse properties and applications;
novel polyamides and methods of producing polyamides.
Safety and Resistant Materials
Nowadays different cut-resistant and bullet-resistant
materials, including personnel, structure and vehicle appli-
cations can be manufactured from m- and p-aramids, due to
the high tensile strength and modulus of these polyamides.
In this same field, Hu and Smith [16] have described a
composite material comprising single-wall carbon nanotubes
and PPPT which upon solution may be spun into fibers or
cast into films. The authors state that the carbon nanotube-
aromatic polyamide composite can be used in applications
which require high tensile strength and modulus, i.e. as
structural reinforcement materials to be used in ballistic
protection where the material has to absorb the impact of
projectiles, shrapnel or other fragments. In the same vein,
over five years ago Kim [17] reported on stabproof and
bulletproof panels for the manufacture of bulletproof vests
made partly of aramide woven fabrics, and Chitrangad [18],
on a combination of p-aramid fiber sheets and compressed
pulp sheets to improve wearer comfort and flexibility in
ballistic-proof materials. Along similar lines, though a little
later, Manten [19] described the preparation of cut-resistant
articles made of aromatic polyamide microfibers. More
recently, Böttger et al. [20] detailed a procedure to produce
hydrophobically finished aramid fabrics, the purpose of
which is to capitalize on the antiballistic properties of
aramid-finished fiber materials in the wet state. The aramid
yarns include an antistatic agent, a lubricant, and a water-
repellent agent.
There is also considerable interest in manufacturing
materials that are highly resistant to wear and creep in both
dry and oily environments. Yamamoto and Fukuchi [21]
have recently described a composition with these charac-

Table 1. Properties of Commercial Polyphthalamide, Poly (Amide Imide) and Wholly Aromatic Polyamides

Polymer Tg, ºC Tm, ºC Characteristics, Processing Methods and Applications

PPPTA -- > 500 d$, hc$ Spun into fibers that can be used as such, ropes or fabric, or as an ingredient in high performance
composite material.

PMPIA 275 365 d$, c$ Spun into fibers, it is sold in both fiber and sheet forms and is used as a fabric wherever resistance
from heat and flame is required.

Poly(amide imide)& 280 --, a$ Highest performing, melt processable plastic (injection or compression molding). It is processed into
a wide variety of forms: films, fibers coatings, adhesives, etc.

PA 6T 370 d$, hc$ Fibers spun from sulfuric acid have properties on par with Nylon 6,6 fibers and retain strength to
much higher temperatures.
$: Highly Crystalline (hc:); Crystalline (c); Amorphous (a); Decomposes (d).
&: Torlon® 4000T: polyamide-imide is made from trimellitic anhydride chloride and a mixture of aromatic diamines.
194 Recent Patents on Materials Science 2009, Vol. 2, No. 3
teristics comprised of a modified fluoropolymer, non-modi-
fied fluoropolymers, and meta or para aromatic polyamides.
One of the key characteristics of the aromatic poly-
amides, and their applications in these fast-growing fields is
that the polyamides employed in flame-retardant or flame-
resistant articles, such as electrical and electronic parts that
require electrical insulation, are either meta and para
aramides, or even semiaromatic polyamides. Excellent heat-
resistance and flame retardant properties have been achieved
using aromatic or partially aromatic polyamides with
halogens containing flame retardants [22, 23], or even with
phosphorous derivatives in order to avoid the use of halogen
compounds which could generate harmful gases on exposure
to fire [24-26].
Zhu et al. [27] have described a yarn for use in arc-
welding and flame protection fabrics with resistance to tears
and abrasion that comprises a modacrylic, p-aramid and m-
aramid fiber. Five years ago, Ghorashi et al. [28] reported on
wicking fabrics comprising aramid crystallized yarns that are
particularly useful in protective garments, i.e. for firefighters,
etc.
Nowadays, the aeronautic industry is demanding light-
weight, flexibility and flameproof materials for aircraft
construction. Along these lines, Forsten and Khan [29] have
reported a flame barrier paper, based on PMPI fibrids and
mica, which meet these requirements.
Membranes
A major application of aromatic polyamides has for
many years been in the field of reverse osmosis membranes.
The aromatic polyamide, which forms the active layer,
shows high salt rejection, high water permeability and high
fouling tolerance [30]. The thin layer is obtained by
interfacial polycondensation of trimesoyl chloride with meta-
phenylene diamine, and polymerization takes place on a
microporous polysulfone membrane. Among their other
applications, these membranes are used in waste-water
treatment, desalination of sea water and dialysis.
Improvements in flux and salt retention are currently
major topics in this field. Ho has very recently added
bifunctional hydrophilic and reactive additives to aromatic
and/or aliphatic crosslinked polyamides [31] in a bid to
improve these properties.
Likewise, Singh and Shah [32] have described a poly-
amide nanofiltration membrane comprising an ultrafiltration
membrane that consists of a polyamide-coated layer made of
wholly or semiaromatic polyamide membranes formed from
meta-phenylenediamine or piperazine and trimesoyl
chloride. This membrane is useful for the removal of phos-
pholipids. Also quite recently, Koo and Hong [33] have
described a similar reverse osmosis membrane, in which the
active polyamide layer was treated with compounds with
iodine atoms in order to covalently anchor the iodine to the
chemical structure of the polyamide. The polyamide mem-
brane was designed to show high boron rejection. Composite
membrane compositions showing high salt rejection rates
have been obtained from polyfunctional compounds in the
form of dendritic polyamides dendrimers, as described by
Ryu et al. [34]. These membranes can be used for industrial
García et al.
ultrapure water production and water purification. According
to Hachisuka and Ikeda [35], coating the active polyamide
layer of reverse osmosis membranes with poly(vinyl alcohol)
allows the practical desalination at a relatively low pressure
showing high salt rejection and high fouling tolerance.
One of the problems of the aramide thin layer of the
reverse osmosis membranes is its relative low resistance to
chlorine. Approximately ten years ago, Kim et al. [36]
reported on membranes with active thin layers comprised of
aromatic polyester or copolymers of aromatic polyester and
aromatic polyamides. These membranes showed improve-
ments in durability due to higher chlorine resistance and
oxidation stability, and better performance related to water
permeability and salt rejection rates.
Much more recently, Ekiner and Simmons [37] reported
on membranes used to separate fluids for the production of
oxygen-enriched air, nitrogen-enriched air, for the separation
of carbon dioxide from hydrocarbons, and the separation of
hydrogen from various petrochemical and oil refining
streams. The membranes are made with blends of poly-
amides, polyimides and polyimide-amide polymers, Scheme
(5). They show high strength, chemical resistance, and are
suitable for high pressure and temperature applications.
Membranes are also used in medicine for dialysis. In this
regard, Takai et al. [38] have recently described a partially
aromatic biocompatible porous membrane, which can be
used for medical purposes as a sterilizable dialysis mem-
brane.
Biomaterials and Polyamide Systems for Medical
Applications
Aromatic polyamides can also be used in medical appli-
cations such as prostheses and artificial implants.
Demakas and Johnston [39] have demonstrated that
screws, hooks, plates, pins, cages, rods, knee and hip
replacements can all be manufactured with para-aramids
instead of metal alloys, thereby avoiding problems that relate
to scattered radiation during diagnosis examinations or
security screenings.
Among other polymers, Johnson [40] has described the
use of aromatic polyamides to prevent damage to a mesh-
reinforced catheter balloon for the treatment of blood vessel
abnormalities.
Polyamides, such as polymers with the amide linkage,
can be formulated to mimic the natural behavior of hair, even
in the presence of humidity. Shirakashi et al. [41] have very
recently reported on partially aromatic polyamides con-
taining hexamethylene diamine and terephthalic acid
monomers used together with an aliphatic polyamide in
artificial hair and wigs.
In the treatment of disease, Sugiyama et al. [42] have
developed a pyrrole-imidazole polyamide with the ability of
alkylating and recognizing a specific DNA base sequence.
This occurs via a vinyl linker at the end of the pyrrole-
imidazole polyamide that has a cyclopropylindone, which in
turn allows gene-level anticancer drug development for the
inhibition of the expression of a specific gene.
Recent Patents on Aromatic Polyamides Recent Patents on Materials Science 2009, Vol. 2, No. 3 195

CO CONH R NH N R NH
CO
O

X
X X1 X X

SO2
X1 X3 S
X2 X3 O O
X2
R:

X X1 X X X1 X1 X X X1
X1

R'

X2
X2 X3 X3 X2 X2 X3 X3 X2

X1 X X1 X X X1
O
R':
O O O O
O
X2 X3 X2 X3 X3 X2

X, X1,X2,X3: Hydrogen, or an alkyl group having 1 to 6 carbon atoms

Scheme 5. Selected chemical structures of polyamides and poly(amide imide)s described by Ekiner and Simmons [37].

preferably at 200ºC or higher for several minutes or for as

Optical Devices
According to Moriyama and Tsukuda [43], the wave-
length-dispersion properties of materials such as poly-
carbonates that have been used in optical devices are unsatis-
factory. Neither polyimides, which show good thermal
resistance, nor para oriented aromatic polyamides can be
used for optical uses, due to their respective brownish and
yellowish colors. Nevertheless, the same authors have
claimed that copolyamides comprising a combination of
structural units, Scheme (6), have high thermal resistance,
high transparency and high rigidity, and can therefore be
used in optical devices. Light transmittance of polyamides
and polyamide films can be controlled through a careful
design of the polymer structure, and it is 80% or more for all
light wavelengths ranging from 450 to 700nm. Thus, its use
is possible in various optical devices such as retardation
plates and protection films.
More recently on the same subject, Oh [44] has described
materials to produce optical films that use aromatic
polyamides, Scheme (7). Flexible displays use polymer films
as substrates, for which purpose polyamides are satisfactory
materials due to their high strength, high elasticity, high heat
resistance, insulating properties and low moisture and gas
permeability. These properties are needed in order to obtain
electrodes on a transparent substrate by conventional ITOs.
Electrode formation is performed at 180ºC, at least, and
long as 30 min.
Suh et al. [45] have reported on the preparation of
poly(amide imide)s for optical communications, i.e. for core
of optical fibers. The polymers show minimum light
absorption loss at a near-infrared light wavelength, high
thermal stability and excellent film processability. These
polymers have a higher refractive index than conventional
fluorinated poly(amide imide)s. Scheme (8) depicts example
structures claimed in the invention.
Hasegawa and Nagasawa [46] have described an image
forming roller employed in the image forming unit which
operates in photocopiers or printers. The roller includes a
shaft made of composite resin containing aliphatic-aromatic
polyamides, glass fibers, and electrically conductive
material, the polyamide having m-xylylenediamine and
,-
aliphatic dicarboxylic acid units. As stated in the patent, the
material exhibits a bending strength of 250MPa and a
flexural modulus of 15GPa.
Hsu and Hsu [47] have shown that Kevlar can be used to
coaxially cover the optical core wire in an optical fiber,
which increases its anti-twist action and tensile strength,
adding further value to the optical fiber.
The photoalignment material for liquid crystal display
films used in cell phones, notebook computers and wide-
screen televisions can be made of aromatic polyamides.
196 Recent Patents on Materials Science 2009, Vol. 2, No. 3 García et al.

(R3)4 (R4)4 R5 R6 (R11)4 (R12)4

R1 R10
HN NHCO R2 CONH NH NHCO R9 CO NH R13 R14 NHCO R15 CO NH R16 NHCO R17 CO

(R7)3 (R8)3
l m n o

R1: O

N
N

R R R
F3C CF3

R2:
R R
R R
R
R: H, D, haogen, aromatic group, hydrocarbon
or halogenated hydrocarbon having a carbon
number of 1 to 5.

R10: SO2 O C(CF3)2 C(CCl3)2 CF2 CCl2 CBr2

R3, R4, R7, R8, R11, R12: arbitrary group.

R9, R15, R16, R17: aromatic group.

R13, R14: linked directly or a group having carbon numer of 6 to 12 which has at least a phenyl group.

Scheme 6. Representative chemical structure of copolyamides claimed by Moriyama and Tsukuda [43].

HN NHCO R2 CO
R1

R3 R4

SO2 SO CH2 C(CH3)2

R 1:
C(CF3)2 CONH NHCO

H F Cl NO2 CN
R3, R4:
CF3 O(CH2)nH n=1-4

R 2:

Scheme 7. Examples of polyamide structures described by Oh [44] to produce optical films.

Different patent claims describe aromatic polyamides, reflectors in light emitting diodes (LEDs), which also serve
Scheme (9), for this purpose, showing the materials low as a housing, and as a transparent sealant for the semi-
residual effect, strong anchoring energy and high thermal conductor. In the same vein, Crowe and Saito [51] have
stability [48, 49]. more recently reported on composite materials that are
suitable for manufacturing reflectors. The composite compo-
Electric and Electronic Devices sition comprised a low amount of aromatic polyamides.
The demand for lighter, thinner and more compact LEDs and other electric and electronic devices need
electrical and electronic goods is increasing day by day. thermally conductive and electrically insulating materials.
Polymers, or polymer composites, are suitable materials for Martens and Topoulos [52] have recently described a
these applications, which moreover require high-perfor- semiaromatic polyamide that acts as a thermally conductive
mance materials that can undergo injection molding and material composite, and have claimed these composites as
have sufficient heat resistance to withstand surface mounting components in light emitting diode assemblies, and Kitani et
technology. On this point, Oka et al. [50] described partially al. [53] has also reported on the use of semiaromatic
aromatic polyamides with a white pigment for use as polyamides in LEDs packages.
Recent Patents on Aromatic Polyamides
X3 O O
X2
C C
O X1 O O
R, R': Yn Yn
Z
X, Y: -NO2, -OR'', -SR'' (R'' is halogenated alkyl or aromatic ring groups).
Scheme 8. Example structures of poly(amide imide)s [45].
H2N
R1
R1, R2, R3: CH2 CH
in combination with H, halogen, cyano, nitro, amino, alkyl, haloalkyl, cyanoalkyl, nitroalkyl, etc.
HN
NHCO
R1
Scheme 9. Diamines described by Shin et al. [48] for the production of photoalignment materials (top), and polyamide structures described
by Kwon et al. [49] (bottom).
Over a decade ago, Yamada and Nakatani [54] described
meta or para-aramid films, and chlorine substituted PPPT,
containing organic or inorganic micro-particles to be used as
materials for a magnetic tapes, photographic films, printer
ink sheets, solar cell base films, substrate for a flexible
printed circuits, electrical insulation capacitor films, etc.
More recently, Handa and Oya [55] have reported on the
preparation of wholly aromatic polyamide films with
microdomain structures, having sizes of 5-600nm, to be used
in printed circuit boards and magnetic recording media. The
films are obtained by casting film-producing dope, a
coagulating process, a water-washing process and a drying
process.
Wholly aromatic polyamides are easily transformed into
aramid paper. Short fibers, pulp, and polymer particles of
aramid swollen with water serve as the starting material.
Murayama et al., Wada et al., Shinohara and Takahashi, and
Iwama and Takahashi have all described the application of
aromatic poylamide synthetic paper sheets as insulating
materials which show high heat resistance, heat dimensional
stability, plybond strength for electric circuits, chip parts,
resistors and the like. The composition of these polyamides
is normally para-oriented aromatic [50-60]. In some cases, a
Recent Patents on Materials Science 2009, Vol. 2, No. 3 197
X3
X2
N R N
NH R' NH
X1 O
Yn Z: SO2 CO O S
(OT)m (T = halogenated alkylene of arylene groups)
Yn: halogen, halogenated alkyl group, halogenated alkoxy group,
halogenated aromatic ring group, -NO2, -OR'' and -SR'' (R'' is
an halogenated alkyl or halogenated aromatic ring group)
NH2 H2N NH2
R2 R3
O COO OCO NHCO CONH
CO
R1, R2: H, Cl, CN, CF3, OCF3, alkyl, oxyalkyl
R2
mixture of meta and para-aromatic polyamides together with
other materials such as glass fiber or PET are used for the
same purposes, as has been reported by Idemura and
Haraguchi, Miyabo, Levit, Wang and Tao, Kawka et al., and
Bersted and Bishop [61-66].
A step forward in the use of polyamide paper is described
by Hartzler [67]. The patent claim describes an electrically-
conductive para-aramid pulp, based on a mixture of para-
aramide and sulfonated polyaniline, to be used as a
reinforcement material with extremely effective electrical
charge dissipation properties, as this pulp shows high surface
area, a high concentration of fibrils and a high modulus.
Aromatic polyamides have also found an application in
printed circuit boards. Some years ago, Shinohara and
Takahashi [68] described a porous para-oriented aromatic
polyamide film, impregnated by a thermoplastic or thermo-
setting, to be used as a substrate for printer circuit boards.
Subsequently, Akatsuka et al. [69] described aromatic
polyamide films or resins, prepared with epoxy resins and
organic solvents, from the hidroxy phenolic group, which
show low-thermal linear expansion, heat and tear
propagation resistance, and adhesion, and which are light
weight, and suitable for use in double-sided flexible printed
198 Recent Patents on Materials Science 2009, Vol. 2, No. 3 García et al.

boards. A recent variant of this application included the use O

of polyamide-imide resins, Scheme (10) and Scheme (11), as
claimed by Chen and Warkoski [70, 71], by Takeuchi and
Tanaka [72], by Kurita et al. [73] and by Shinada et al. [74].
Takeuchi et al. [75, 76] have reported on the preparation
of siloxane-modified poly(amide imide) resin compositions
to produce adhesive films useful for the production of
semiconductor devices. Schemes (10) and (12) depict the
structure of selected monomers employed in the synthesis of
the polymers.
Data storage is currently of great interest in scientific and
industrial research. Para-oriented aromatic polyamides can
provide films for high-density magnetic recording media.
Films of this type show strength, slipperiness and winding
and handling properties, and are useful as a base film for
magnetic conversion characteristics; audio drop-out,
repeated running properties and durability all being excel-
lent. These films are thinner and stiffer than polyester, and it
is preferable for some of the hydrogen atoms of the aromatic
rings to be substituted by halogens, nitro, ethyl, alkyl or
alkoxy groups [77-79]. For example, Usuki [80] described a
floppy disk showing low susceptibility to warping and
smooth surfaces that can be manufactured with this film.
R1 R2
N NH
CO
O
R1, R2: H, C1-4 alkoxy or alkyl
Scheme 11. Structure of poly(amide imide)s described by Kurita et
al. [73].
Sezi [81] has described a photosensitive formulation for
forming microelectronics. High heat-resistant photosensitive
films made of polyhidroxyamides are transformed into
polybenzoxazole films, suitable for microelectronics as
dielectrics or buffer coatings. Likewise, Nakamura [82] has
reported on poly(amide imide)s used as binders in the light-
heat conversion layer of a heat transfer sheet to form a full
color image with high resolution in laser thermal transfer
recording, Scheme (13).
Aramid-like polyamides have found applications in
batteries. Thus, in each of the organic electrolyte secondary
batteries, i.e. lithium ion batteries, a porous polymeric film
allows ions to flow together with the electrolyte between the
positive electrode and the negative electrode. Meta and/or
para aromatic polyamide films are also used as second

O O

N R N
HOOC COOH CH3
O O C SO2
CH3

CF3
C CH2
CF3
R: O X O X:

CO

O O

N R' N
HOOC COOH
O O

R3 R5
R': R1 Si O Si R2 R1, R2, R3, R4, R5, R6: alkyl, phenyl, or substitued phenyl group
R4 R6
n

Scheme 10. Diacid moieties of poly(amide imides) described by Takeuchi and Tanaka [72] and by Shinada et al. [74].
Recent Patents on Aromatic Polyamides Recent Patents on Materials Science 2009, Vol. 2, No. 3 199

O O
R3 R5 R3 R5
N R1 Si O Si R2 N H2N R1 Si O Si R2 NH2
HOOC R4 R6 COOH R4 R6
n n
O O

R1, R2, R3, R4, R5, R6 : alkyl, phenyl, or substitued phenyl group

Scheme 12. Selected structures of siloxane-modified poly(amide imide)s [75].

N R NH
CO
O

R: O S

CF3
C CH2 SO2
CF3

O O O O O

O O O SO2 O

CH3 CF3
O C O O C O
CH3 CF3

H3C CH3 H3C CH3

CH2

H3C CH3 S
O O
X X Y Y

CH2 X: halogen Y: OH, CH3, OCH3

Scheme 13. Structure of the poly(amide imide)s described by Nakamura [82].

battery separators, because they can be thinned, their energy
density increased, and because they have high resistance to
short-circuiting and exhibit stable porosity properties (to
enable ions to flow together with the electrolyte between the
positive and the negative electrodes) over long periods of
time [83-85]. Shigematsu et al. [86] have recently described
a non-woven fabric for alkaline battery separators, made of
partially aromatic polyamide film, with superior alkaline
resistance, enabling rapid charging and large current dis-
charging, while maintaining the above-mentioned properties.
Previously, Liener et al., König et al., and Studer et al.
all described wire enamels with improved adhesion which
are used for coating metal wires (particularly cooper wires),
using enamels containing polyamide-imides and/or poly-
esterimide as binders. The aforementioned poly(amide
imide)s are formed from polyoxyalkylenediamine mono-
meric building blocks [87], from aromatic imide- and amide-
forming components with aromatic polycarboxylic acid
derivatives [88], and from modified diisocyanates [89]. A
review of wire enamels with excellent thermal and chemical
properties has recently been published by Murray [90].
200 Recent Patents on Materials Science 2009, Vol. 2, No. 3
The use of aramid fibers has also been extended to the
production of high performance loudspeaker diaphragms and
housings for electronic equipment. The fibers can be
dispersed in an injection-moldable thermoplastic resin to
improve internal loss in loudspeaker diaphragms [91]. A
mobile telephone housing was also described by Topoulos
comprising a partially aromatic polyamide composition
having excellent stiffness and low-moisture absorption [92].
Architecture Materials
Partially aromatic polyamides resins are widely used in
automobile, aircraft and building devices such as fuel tubing,
joints, tires, etc. Common features of the semiaromatic resins
described in this section are their moldability and recycl-
ability along with high levels of residence stability, heat
resistance, chemical resistance, excellent adhesive proper-
ties, compatibility with other resins, small fuel permeation,
excellent stiffness and fuel barrier properties. Thus different
patents describe the use of the partially aromatic polyamides
for vehicle tubes, i.e. tubing used in vacuum brake systems,
as fuel barriers, as connectors for fuel lines, as joints for fuel
tanks, or the like. [93-99].
Most recently Nozaki and Huroe [100], and Nakamura
and Miyamoto [101] have all described the application of
partially aromatic polyamide resins for use in welding, as
these materials have excellent flowability upon molding,
heat and hydrolysis resistance, high cycling properties and
show high weld strength and mechanical properties, and can
therefore be used, for example, in automobiles or electrical
parts.
Fujii and Sarukawa [102] have reported on glass fiber-
reinforced thermoplastic resin made of a partially aromatic
polyamide, which has increased strength and rigidity and
excellent characteristics such as impact resistance and
antifreeze liquid resistance, and may be used in machine-
related materials, home equipment, automobiles and the like.
Very recently, Bellet et al. [103] have described partially
aromatic polyamide hoses for delivering compressed air to
equipment, machine tools and various other devices and also
in brake circuits in high-power vehicles, the polyamides
being polyisophthalamides and polytherephthalamides, or
blends of both or copolymers.
Aramid fibers are commonly used as reinforcing fibers in
high performance composites, i.e. in vehicles and aircraft
tires, intended to support heavy loads and inflated to
relatively high pressure. Thus, Harikae and by Westgate et
al. [104, 105] claim that they may be used as a substitute for
nylon in pneumatic radial tires, because they achieve
superior cord extensibilities while meeting specifications for
deflection and heavy load, they increase circumferential
rigidity, and reduce road noise.
Honeycombs are key structures in the aeronautics
industry. Comprising a supporting base of glass fiber imp-
regnated with a poly(amide imide) resin prepolymer, they
have excellent mechanical strength and heat formability to
curved surfaces and are used in engines for airplanes and
space machinery exposed to high temperature and pressure
[106]. The poly(amide imide) structures are based on
trimellitic anhydride and 4,4’-diaminodiphenyl methane.
García et al.
Nomoto [107] also described a method for producing
honeycomb structures from aramids.
Packaging Materials, Filters, Gas Barrier Films and
Coatings
A huge number of materials are used in industry for
cheap packaging. The need for higher performance, regar-
ding mechanical properties or gas barrier properties, is
moving applied research toward novel composites and even
multilayer materials. Resins, films or composites made of
aromatic, aliphatic, or partially aromatic polyamides, a
mixture of them or in combination with other copolymers,
i.e. polyethylene terephthalate [108], or made of organically
modified phyllosilicates [109], etc. have all been described
as packaging materials with good gas barrier properties, high
strength, elastic modulus, hydrothermal resistance, trans-
parency and good adhesion to other polymers. These films
are suitable for food, toothpaste, chemical and medical
products, drug packages, bottles and bags [110-116].
Filters represent another important product in industry.
Kohli et al. [117] have described tubular bag filters with
enhanced filtration performance, particularly useful in
filtering hot gases, i.e. gases at temperatures of 150ºC or
even higher. The bag filters are fabricated with intimate fiber
blends of meta-aramid fibers and acrylic fibers. The filters
could be useful for hot gases to remove particulate matter
from asphalt, coal plants and other industrial concerns,
contributing to environmental protection.
As a curiosity, a few years ago Kennedy et al. [118]
reported on a golf ball cover and/or core which combines an
ionomer and a polyisophthalamide, resulting in improved
toughness, durability, stiffness, hardness, and fatigue
resistance over a broad temperature range.
Fibers, Resins and Films with Diverse Properties and
Applications
Partially aromatic polyamides are semicrystalline or
amorphous which show heat resistance, good mechanical
properties, chemical resistance, dimensional stability, low
moisture absorption, good processability, and mechanical
strength, and transparency, etc.
Takiue and Fujita [119] have very recently described a
wholly meta-aromatic fiber with excellent high-temperature
processability, obtained by wet spinning, capable of provi-
ding products with high performance, and high quality,
which can even be made colorless, by subjecting the fibrous
material to saturated steam treatment and then to heat
treatment.
Earlier on, Elkovitch et al. [120] described the
preparation of a poly(arylene ether)/polyamide composition,
wherein the polyamide comprises terphthalic acid and 1,9-
nonanediamine and/or 2-methyl-1,8-octanediamine units.
The blends have a combination of high heat resistance,
processability, comparable dimensional stability in the flow
and non-flow directions in the absence of filler, and low
water uptake.
Over a decade ago, Gottschalk et al. [121] reported on
the preparation of thermoplastic molding materials con-
Recent Patents on Aromatic Polyamides
taining semiaromatic polyamide/polyolefin blends, which
included compatibilizers and could be transformed into
fibers, films and moldings.
Lapierre [122] described fabric blends of aramid fibers
and flame resistant cellulosic fibers. Both kind of fibers are
dyed and can be finished in the conventional manner. The
finished process can include the application of wicking
agents, water repellents, stiffening agents, softeners, and the
like.
Nozaki et al. [123] claimed polyamide compositions for
molding, the composition of which comprises fibrous
wollastonite and semiaromatic polyamides with superior
rigidity, strength, toughness, dimensional stability, chemical
resistance, external surface appearance and sliding charac-
teristics in high-humidity, high temperature environments,
having a low linear-expansion coefficient and low warpage.
Moreover, the properties of the polyamide compositions are
maintained in recycled objects. Ogo and Shiomura [124]
have reported on semiaromatic polyamide pellets suitable for
use in molding material for forming miniature parts for
motor vehicles and electrical or electronic equipments, the
polymer comprised of terephthalic acid or other aromatic
acids and C4-12 aliphatic diamines. Likewise, Amimoto et
al. [125] have described semiaromatic polyamide resins with
a similar composition, which show excellent metal mold
ejectability during molding operations, and are very useful
for producing such products as connectors for electrical
devices, electrically-driven tools, housing for printed wiring
boards, etc.
Oka et al. [126] have claimed semiaromatic polyamides
as molding materials to produce articles used at high
temperature, such as automobile engine room parts and
household goods. The polyamide composition was aromatic
dicarboxylic acids and various diamines, i.e. 1,9-non-
anediamine, 2-methyl-1,8-octanediamine, 3-methyl-1,5-pen-
tanediamine, 2,4,4-trimethyl-1,6-hexanediamine, etc.
Montal et al. [127] described the preparation of poly-
phthalamide compositions with improved toughness com-
prising polyamides and a modifying component comprising
styrene polymer blocks and rubber blocks. The compositions
are claimed to be useful for fabrication of such articles as
automotive under-the-hood parts and other appli-cations
requiring high toughness, strength, and thermal resistance.
Following a similar strategy, Hewel [128] has recently
described semiaromatic polyamide molding compositions
based on blends of polyamides 10T and 6T with reinforcing
materials, i.e. glass and or carbon fibers, and additives,
consisting of impact modifiers, adhesion promoters or
compatibilizers, lubricants, crystallization accelerators or
retarders, mold release agents, etc. They serve as sintering
powder in molding compositions for the production of
thermoplastically processable molded items, such as parts for
pumps, gearboxes, valves and water meters, throttle valves,
cylinders, pistons, headlamp casings, reflectors, gearwheels,
connectors, electronic components, fluid conducting lines,
etc.
Along similar lines, a few years ago Ebert et al. [129]
and subsequently Rulkens et al. [130] described filled
polyamide molding materials with improved processing
Recent Patents on Materials Science 2009, Vol. 2, No. 3 201
behavior. The polyamide compositions are made of semi-
crystalline semiaromatic homo or copolyamides blended
with non-crystalline or low-crystalline homo or copoly-
amides. Topoulos [131] has reported on materials made of
semicrystalline semiaromatic homo or copolyamides blended
with impact modifiers, i.e. ethylene polymers, grafted
styrene thermoplastic elastomers, olefin/acrylic acid/dicar-
boxylic acid terpolymers, etc. and stabilizers, i.e. phosphites,
phenols or amines. All these polyamide compositions are
described as molding materials for use in telecommu-
nications, transport, furniture, sports, apparatus engineering,
machine construction, heating installation, air conditioning,
sanitation, tools, etc.
Elia et al. [132], and Uchida and Hara [133] have all
reported on semiaromatic polyamide composites for use in
automobile parts such as seat frame components, engine
cover brackets, spare tire wells, door systems for cars,
housing for transmission and power delivery components, oil
pans, airbag housing canisters, automotive interior impact
structures, cross car beams, pressure vessels such as
refrigerant bottles and fire extinguishers, vehicle wheels,
baseball bats, hockey sticks, ski and snowboard bindings and
bicycle frames, belt chains, radiator tanks, engine mountings,
automobile fans, oil strainers, cylinder head covers, fuel
filters, inlet manifolds, air ducts, junction box and wire
harness connectors, lamp reflectors, and electronic parts such
as connectors, switches, volumes, bobbins and household
goods. The inventions described polyamide compositions
comprising PA 6T, PA 12T, PA 10T, PA9, T copolymers
with aliphatic PAs, reinforcing fibers (glass, carbon and
aramid fibers), etc.
Transparency is not usual in polyamide compositions due
to the crystallization tendency of the aromatic or semiaro-
matic polyamides. Montanari and Recoquille [134] have
reported blends of semiaromatic polyamides and aliphatic
polyamides for the production of transparent objects by
injection molding such as plates, laminates, tubes, profiles
and decorated articles by sublimation. With regard to
transparency, a few years ago Bühler [135] reported that the
addition of phosphorous compounds during the extrusion of
blends of amorphous and partly crystalline polyamides gave
rise to highly transparent polyamide blends with improved
stress cracking resistance. Cheng [136] has also reported on
transparent semiaromatic polyamide composition with
improved light transmittance properties, suitable for sight
windows for tanks or reservoirs for fuel and oils, where the
polyamide was comprised of copolymers or blends of
common PAs: PA 6T, PA 12T, PA 10T, PA9, T aliphatic
polyamides, isophthalic containing polyamides, etc. The
patent claim describes partially aromatic polyamide mixtures
or alloys having improved transparency, chemical resistance
and a slight natural color, suitable for use in rods, spectacles,
lenses, lamps, mirrors, panes, sight glasses, optical compo-
nents, containers, medical, cosmetic and hygiene articles,
tooth-brushes, fashion jewelry and other applications.
Takaragi [137] has claimed a resin composition for
bonded magnets comprising magnetic particles and partially
aromatic polyamides, which exhibit excellent mechanical
strength and heat resistance.
202 Recent Patents on Materials Science 2009, Vol. 2, No. 3
Conley et al.,[138] have recently described the process of
making meta and para-aramid pulp, which can be used as
reinforcement in the production of friction and sealing
materials such as friction modifiers, fillers, binders and the
pulp itself. Likewise, Hikichi et al. [139] have reported on
the preparation of friction materials for brakes or a clutch
comprising aramide fibers and different inorganic fibers.
Also quite recently, Auza et al. [140, 141] have reported on
wholly aromatic polyamides used for nonwoven materials
comprising fluoropolymer fibers used as liner materials for
self-lubricating bearing surfaces, such as sealants, in
filtration systems and in electrical insulation.
Regarding filament production, Han et al. [142-144] have
reported different spinning procedures to obtain para
oriented aromatic polyamide filaments with high strength,
high modulus and high crystallinity. Willemsen and Stuut
[145] have described aramid filament yarn provided with a
conductive finish comprising an organic conductive product.
These filaments can be used for break detectors in elevator
cables, in combination with untreated aramid filament yarns,
or for accessories which have to lay on or to eliminate static
electricity in record players, magnetic tapes, compact disks
and the like.
Poly(amide imide)s have found applications in coating
compositions for use in sliding members in resin containing
a solid lubricant, for friction and wear applications, such as
metal-polymer bushings and bearings, in electrical and
electronic insulation applications, such as wire and cable
tapes, substrates for flexible printed circuit boards, motor
slot liners, magnet wire insulation, transformer and capacitor
insulation, etc [146-149]. The poly(amide imide)s have a
usual chemical composition derived from the polymerization
of trimellitic anhydride acid/chloride and usual diamines or
diisocianates (MPD, PPD, 4,4’-diphenylmethane diisocianate
or diamine, etc.), Scheme (14).
Another use of polyamide-imides is for resin compo-
sitions with molten and sliding properties, strength and
tenacity that are useful in precision molding and thin article
molding. They need to have excellent extrusion moldability
and injection moldability, heat resistance, and flowability.
Yamada et al. [150] have described a resin composition with
such characteristics comprising poly(amide imide)s and
polyarylenes, specifically poly(phenylene sulfide)s. The
patent claims improved compatibility of the systems.
O X
N R N R:
C
O O
CH3
R': SO2 CO C O
CH3
Scheme 14. Poly(amide imide)s.
García et al.
Novel Polyamides and Methods of Producing Polyamides
Currently there are diverse methods for producing
aromatic, semiaromatic and aliphatic polyamides. Never-
theless, the applied research in this field is directed toward
novel, cheaper, simpler, etc. preparation methods, and not so
often toward novel synthetic routes.
A few years ago, Presenz et al. [151] reported on the
reaction of aliphatic or aromatic dicarboxylic acids with
diamines, preferably m-xylylene diamine, in various steps,
being a variation of the usual salt forming method. The
method is distinguished in that polycondensation is carried
out at most 10 bar and at a temperature of 255- 270ºC.
Later on, Etchells and Mallon [152] described the conti-
nuous reaction of dicarboxylic acid halides with diamines in
two stages. The first step is based on an oligomer poly-
merization process in which an aromatic and/or non-aromatic
diamine reacts with an aromatic and/or non-aromatic
dicarboxylic acid dihalide in a polar, non-basic, inert organic
liquid medium under controlled conditions, such that a
condensation product having a low degree of polymerization
is formed (prepolymer). In the second step, the organic liquid
medium containing the prepolymer is contacted with an
aqueous solution of a water-soluble acid acceptor to form a
polyamide product having a high degree of polymerization,
by continuously feeding the prepolymer and the acid
acceptor solutions into a reactor system. This polyamide is
processed into fibers, films, coatings and shaped articles.
Tsujii et al. [153] have reported a method for conti-
nuously producing wholly or partially aromatic polyamides
by melt polymerization using a multistage polymerization
reaction apparatus. The continuous production method
comprises the following steps: (a) a raw-material preparation
step, in which a diamine and a dicarboxylic acid are
individually melted, or a salt of amine and carboxylic acid is
produced in water, (b) a raw-material introduction step,
consisting of continuously introducing the treated raw-
materials into a tubular reaction apparatus, (c) an amidation
step, in which the raw-materials are passed through the
tubular reaction apparatus, to obtain a reaction mixture
containing an amidated product and condensed water, (d) an
initial polymerization step, in which the reaction mixture is
introduced into a continuous reaction apparatus at a higher
temperature than the melting point of the polyamide,
separating and removing the water, and raising the poly-
merization degree to obtain a polyamide preploymer. (e) a
X
R'
X: H, CH3
S
Recent Patents on Aromatic Polyamides Recent Patents on Materials Science 2009, Vol. 2, No. 3 203

final polymerization step in order to obtain a polyamide that
can be adjusted to a desired relative viscosity. This method
gives rise to good quality polymers with excellent mecha-
nical strength and dimensional stability and an especially
stable degree of polymerization. These polyamides are used
for films, sheets, packaging bags, bottles, engineering
plastic, fibers and the like.
Winterling et al. [154] have described the reaction of a
mixture comprising a monomer which has a nitrile group and
another functional group capable of forming a carboxamide
group with water in the presence of titanium dioxide as a
catalyst, yielding aliphatic, semiaromatic or aromatic
polyamides. The process is claimed to be technically simple
and cost-effective.
Murakami et al. [155] have reported the preparation of
wholly or partly aromatic polyamides by melt reaction and a
solid phase polymerization. The process consists of
performing melt reaction of a dicarboxylic acid with a
diamine, thereby giving a low molecular weight condensate,
subjecting it to solid phase polymerization in a vacuum or
under a gas stream, which yields an aromatic polyamide
precursor that is finally subjected to melt polymerization.
This process is supposed to permit the industrial production
of high molecular weight aromatic polyamides in an
economical and efficient manner.
Fowkes [156] has recently described aromatic polyamide
systems using aromatic dicarboxylic acids, Scheme (15), and
heterocyclic diamine precursors, Scheme (16), or reactive
amino-acids heterocyclic precursors, Scheme (17). The
process includes heterocyclic structures that have hetero-
atoms in a position that is beta relative to one or more
reactive amine groups, thus promoting intermolecular
interactions, intra-molecular interactions and/or enhanced
solubility, back-bone rigidity and stability of the polymer
that is formed in this way. This polymer can form extended
linear, curved, circular, coiled or helical structures.
Baek and Tan [157] have reported a method of producing
hyperbranched aromatic polyamides, Scheme (18). The
invention relates to novel amine-terminated hyperbranched
quinoxaline-amide polymers as room temperature initiators

OH HOOC
HO OH HOOC COOH
HOOC COOH
HOOC COOH HO COOH
HO OH
HO OH

OH
HOOC HO OH

HOOC COOH
COOH HOOC COOH
OH OH
OH

Scheme 15. Aromatic dicarboxylic acids [156].

NH2

N N N N
H 2N NH2 H2N NH2
N
N N N H 2N NH2
NH2

N NH2 NH2 N NH2

N N N
N N
H2N N H 2N NH2 H 2N H 2N N

N NH2 N NH2 N N NH2

N N
N N N
H2N H2N N H 2N N H 2N N N NH2

N NH2
N N N NH2
N
N N N
H 2N H2N
H2N
NH2 NH2 NH2

Scheme 16. Heterocyclic diamine precursors [156].

204 Recent Patents on Materials Science 2009, Vol. 2, No. 3
OH OH
COOH COOH
N NH2 H2N N H 2N
OH
NH2
COOH
OH
N
N N
COOH
NH2
Scheme 17. Reactive amino-acid heterocyclic precursors [156].
H H
N O
O O
N
N
N O
H
Scheme 18. Hyperbranched aromatic polyamides.
for bismaleimide polymerization. In [157], a process based
on providing novel quinoxaline-containing AB2 monomers
for hyperbranched polyamides production is set out. Because
of this hyperbranched feature, these polyamides have lower
solution and melt viscosities than their analogs of similar
molecular weights, are attractive in terms of processability
and offer flexibility in engineering-required properties for
specific applications.
Kosaka et al., [158] have described a three-step
economical and efficient process for preparing partially
aromatic polyamides. The first step is the preparation of a
solid low-degree condensation product having an intrinsec
viscosity [
]1 of from 0.05 to 0.2dL/g by polycondensation
reaction of the dicarboxylic acid with the diamine. The
second step is a solid-phase polymerization of the low-
degree condensation product at a temperature no higher than
195ºC to prepare a solid-phase polymerized product having
an intrinsic viscosity [
]2 that satisfies the relation [
]2-[
]1 =
0.02 to 0.1dL/g. The third step is a further solid-phase poly-
merization of the product to obtain an aromatic polyamide
having an intrinsec viscosity [
]3 of 0.15 to 1.1dL/g and a
ratio of [
]3/[
]2 that is no smaller than 1.0.
Liou et al. [159] have reported on the preparation of
novel wholly aromatic polyamides by reacting 1,4-naphthyl
or 2,6-naphthyl containing diacids with various aromatic
diamines. The polymers were readily soluble in polar aprotic
solvents, and could be cast into transparent, tough and
flexible films.
Phillion [160] has described processes for the production
of polyamides containing heteroaromatic amines, such as N-
methylimidazole and N-methylpyrrole. The invention relates
García et al.
OH
OH OH
COOH
COOH H2N COOH
N
N
N
NH2
OH
H2N COOH
N
H2N
COOH
N
N
H
N
to the preparation of aromatic and heteroaromatic acid
halides (see Scheme (19)) and their use in the polyamide
synthesis. This process is twofold, consisting firstly of
monomer and then polymer synthesis. The aminoacid halide
is prepared by reaction of a carboxylic acid with a
-
haloenamine which may or not be immobilized on a support.
In the production of a polyamide oligomer or polyamide, a
member of an aminoprotected amino acid halide building
block unit is then combined with a moiety comprising an
unprotected amino functionality to form a reaction product
possessing an amide linkage and a protected amino
functionality. These polyamides are used as agents for the
control of gene expression. This high efficiency method
provides high yield and pure acid halides, and polyamides
with short coupling times. The stability and simplicity in the
structure of minor groove-binding polyamides makes such
molecules especially suitable for most sequence-specific
DNA-binding applications.
Liaw and Liaw [161, 162] have detailed the preparation
of soluble aromatic polyamides and poly(amide imide). The
polymers are prepared using a diamine 3,3’,5,5’-tetramethyl-
2,2-bis[4-(4-aminophenoxy)phenyl]propane and 2,2’-
dimethyl-4,4’-bis(4-aminophenoxy)biphenyl, Scheme (20),
to prepare high performance soluble engineering plastics by
polycondensation. The incorporation of bridges between the
phenylene units and tetra methyl substituent on the pheny-
lene units effectively reduces crystallinity and enhances the
solubility of the polyamides and the poly(amide imide). On
the other hand, polymers with methyl substituent on arylene
show excellent thermo-oxidative stability.
Recent Patents on Aromatic Polyamides
R1
X1 N
R3
N X2 COX
R2
X = Cl, Br
X1 = N, CR4
X2 = N, CR5
R1 : H or substituted or unsubstituted C1-C10 alkyl, C2-C10 alkenyl, C2-C10 alkynyl.
R2 and R3: they are independently H or an amine protecting group.
R4: H or a substituted or unsubstituted alkyl group.
R5: H, OH or an alkoxy group.
Scheme 19. Aromatic and heteroaromatic acid halides.
H2N
H2N
Scheme 20. Chemical structure of 3,3’,5,5’-tetramethyl-2,2-bis[4-(4-aminophenoxy)phenyl]propane and 2,2’-dimethyl-4,4’-bis(4-
aminophenoxy)biphenyl.
Ishihara and Yamamoto [163] have reported a process of
preparing aromatic polyamides, polyimides, or poly(amide
imide)s by direct thermal solution polycondensation. In this
case, polycondensation consists of the reaction between a
polyamine and a polycarboxylic acid, using arylboric acids
as polycondensation catalysts and pentamethylbenzenes as
the solvent. The authors describe the advantages of this
method as easy post-reaction product purification, that gives
a high yield free from side reactions, although the poly-
merization temperature is high.
Choi et al. [164] have reported on the preparation of
poly(amide imide)s by direct polymerization. The polymers
were obtained by reaction of a tricarboxylic acid anhydride
and an aromatic diamine to render diimidedicarboxylic acid,
followed by the transformation of the diacid into its diacid
chloride derivative, and finally by a further reaction with a
diamine to produce the polymers. The inventors have also
described poly(amide imide)s, Scheme (21), with a head-to-
tail backbone, providing excellent heat and chemical
resistance, physical and mechanical properties, process-
ability, and gas permeability and selectivity [165].
Xu [166] has reported on the poly(amide imide) com-
positions for magnet wire which exhibit solvent or varnish-
induced craze resistance. The polymer compositions include
a compound selected from the group consisting of diacid
compounds, trimellitic anhydrides, benzophenone-tetracar-
boxylic anhydrides, and mixtures thereof, a diisocyanate
compound, dihydroxyl compound, a trihydroxyl compound,
a fluoropolymer, and a mineral filler.
Recent Patents on Materials Science 2009, Vol. 2, No. 3 205
R1 R11
X1 X1
R3 R3
N X2 COX N COX
X2
R2 R2
X = Cl, Br X = Cl, Br
X1 = N, CR4 X1 = O, S, NR4
X2 = O, S X2 = N, CR5
NH2
O O
O O NH2
Finally, Ng [167] has proposed the preparation of
partially aromatic polyamides by reaction of partially
esterified dicarboxyic acids with aliphatic diamines giving
rise to partially N-alkylated polyamides.
CURRENT & FUTURE DEVELOPMENTS
Aromatic polyamides are unique materials insofar as
their thermal and mechanical behavior is concerned.
However, their extremely high transition temperatures and
their poor solubility in common organic solvents or commer-
cial polyamides, which lie above their decomposition
temperatures, give rise to processing difficulties and limit
their applications. As a consequence, basic and applied
research is being carried out to enhance their processability
and solubility in order to broaden the technological scope of
application associated with these materials. From a research
point of view, these goals have been partly achieved,
although further research is still needed. Moreover, basic and
applied researchers should try to exploit the high perfor-
mance properties of the polyamides in new fields, i.e.
optically active materials [168], photo and electrolu-
minescent materials [169-171], materials with even high
mechanical properties [172], polymers with a controlled
structure [173, 174], biodegradable materials [175], materials
with molecular recognition capabilities [176], etc.
ACKNOWLEDGEMENTS
The financial support provided by the Spanish Ministerio
de Investigación e Innovación - Feder (MAT2008-00946/
MAT) is gratefully acknowledged.
206 Recent Patents on Materials Science 2009, Vol. 2, No. 3 García et al.

O O

CO Ar1 N Ar2 NH Ar1:

O O
O
C O C

O
C

R3 R1

H3C CH3
CH3
O

R4 R2

Ar2: O O O O O
R2 R1
R1,R2,R3,R4:
X
CH3
R4 R3 O SO2 O O C O
CH3

CF3 O
O C O O C O
CF3

X: -O-, -S-, -SO2-, -CO-, -C(CH3)2-, -C(CF3)2-

Scheme 21. Selected structures of poly(amide imide)s [165].

CONFLICT OF INTEREST
As far as we are concerned, there is no conflict of
interest.
REFERENCES
[1] Fink JK. High performance polymers. William Andrew Inc.,
Norwich, 2008.
[2] Rules and Regulations Under the Textile Fiber Products
Identification Act (http://www.ftc.gov/os/statutes/textile/rr-textl.
pdf), Part 303.7 (Generic names and definitions for manufactured
fibers), US Federal Trade Commission (FCT) 2002.
[3] Vollbracht L. Aromatic polyamides comprehensive polymer
science. In: Eastwoond GC, Ledwith A, Russo S, Sigwalt P, Eds.
Allen G, Bevington JC, Chairmans of the Editorial boards.
Pergamon Press: Oxford 1989.
[4] Gaymans RJ. Polyamides. In: Rogers ME, Long TE, Eds. In
synthetic methods in step-growth polymers. John Wiley & Sons,
Inc.: Hoboken 2003.
[5] Elias HG. Macromolecules. Industrial polymers and synthesis.
Wiley-VCH: Weinheim 2007; Vol. 2.
[6] Vollbracht, L., Veerman, T.J.: US4308374 (1981).
[7] Yang HH. Kevlar aramid fiber. John Wiley & Sons: Chichester
1993.
[8] Kathiervelu SS. Aramid fibers. Synth Fib 2003; 32:12-15.
[9] Reboullai S. Aramids high-performance fibres. In: Hearle JWS, Ed.
Woodhead Publishing Limited series on fibres. CRC Press: Boca
Raton 2004; pp. 23-61.
[10] Gabara V, Hartzler JD, Lee K-S, Rodino DJ, Yang HH. Aramid
Fibers. Handbook of fiber chemistry. In: Lewin M, Ed.
International fiber science and technology series. 3rd ed. CRC
Taylor & Francis 2007; Vol. 16: pp. 975-1029.
[11] Reisch MS. High-performance fibers find expanding military,
industrial uses. Chem Eng News 1987; 65(5): 9.
Recent Patents on Aromatic Polyamides Recent Patents on Materials Science 2009, Vol. 2, No. 3 207

[12] Nomex® 40th Anniversary, Du Pont. http://www2.dupont.com/ [70] Kurita, T., Suzuki, S., Inukai, C.: US20087364799 (2008).
Nomex/en_US/news_events/40th_anniv.html [71] Chen, H., Warkoski, G.: WO2007054543 (2007).
[13] Lubowitz, H.R., Sheppard, C.H.: US5969079 (1999). [72] Takeuchi, K., Tanaka, Y.: US20067138174 (2006).
[14] Murria TJ. Poly(amide imides): Wire enamels with excellent [73] Kurita, T., Suzuki, S., Inukai, C.: US20087364799 (2008).
thermal and chemical properties. Macromol Mater Eng 2008, 293: [74] Shinada, E., Kanno, M., Tsuru, Y., Horiuchi, T.:
350-360. US20006121553A1 (2000).
[15] Standard Specification for Polyphthalamide (PPA) Injection [75] Takeuchi, K., Saito, T., Nanaumi, K.: US20016252010 (2001).
Molding Materials (ASTM D5336-03) in ASTM Book of [76] Takeuchi, K., Saito, T., Nanaumi, K.: US20026475629 (2002).
Standards, ASTM international, Plastics (III), West Conshohocken, [77] Hanada, M.: US20006124021 (2000).
Pennsylvania, 2008; Vol. 08.03:. DOI: 10.1520/D5336-03. [78] Handa, M., Ono, M., Asai, T.: US20026344257 (2002).
http://www.astm.org/Standards/D5336.htm [79] Sueoka, M., Horiuchi, M., Tsukuda, A.: US20026358619 (2002).
[16] Hu, X., Smith, K.A.: US2004022981 (2004). [80] Usuki, K.: US2002028354A1 (2002).
[17] Kim, J.-O.: US2002173210 (2002). [81] Sezi, R.: US20056884567 (2005).
[18] Chitrangad.: US20006030683 (2000). [82] Nakamura, H.: US20056936397 (2005).
[19] Manten, J.: US20046829881 (2004). [83] Sueoka, M., Nishihara, K., Tsukuda, A.: US2008113177A1 (2008).
[20] Böttger, C.K., Hartert, R., Stolze, K.R., Pager, J., van de Ven, H., [84] Ohno, T., Sadanobu, J., Nakamura, T., Honda, S., Ishiwata, T.:
Akker, P.G.: US20067132131 (2006). US20087407702 (2008).
[21] Yamamoto, Y., Fukuchi, E.: US2008300366 A1 (2008). [85] Kikuchi, T., Shimozono, K., Fujisawa, C., Tomimoto, K.:
[22] Bersted, B.H., Reichmann, M.G.: US20036531529 (2003). US2008206646A1 (2008).
[23] Akagawa, Y., Ube-Shi, Y.: EP0960910 (1999). [86] Shigematsu, T., Maeda, S., Katayama, T.: US20087405172 (2008).
[24] Martens, M.M., Saga, Y.: US20077294661 (2007). [87] Liener, K.-W., Schmidt, G., Lehmann, H.: US20016316046 (2001).
[25] Marvins, M.M., Saga, Y.: WO2005033192A1 (2005). [88] Studer, V., Piechaczyk, A., Schildknecht, L.: US2006122353A1
[26] Yabuhara, T., Tada, Y., Nakano, S., Kameshima, T., Nishikota, Y., (2006).
Takase, H.: US20036521689 (2003). [89] König, S.T., Lienert, K.W., Schmidt, G.: US20067122244 (2006).
[27] Zhu, R., Guckert, D., Lovasic, S.L.: US20067065950 (2006). [90] Murria TJ. Poly(amide imide)s: Wire enamels with excellent
[28] Ghorashi, H.M., Routhier, D.: US20036607562 (2003). thermal and chemical properties. Macromol Mater Eng 2008; 293:
[29] Forsten, H.H., Khan, S.: US20016312561 (2001). 350-360.
[30] Cadote, J.E.: US4277344 (1981). [91] Tokura, K., Takebe, T., Uryu, M., Tagami, T.: US200703444A1
[31] Wiston, H.W.S.: US2008296225A1 (2008). (2007).
[32] Singh, K., Shah, V.J.: US2008135482A1 (2008). [92] Topoulos, G.: US2009005502A1 (2009).
[33] Koo, J., Hong, S.P.: US2007227966A1 (2007). [93] Sato, K., Maruo, K., Mitadera, J., Kurokawa, M.: US20067053172
[34] Ryu, J.H., Choi, S.H., Lee, K.J.: US2008199619A1 (2008). (2006).
[35] Hachisuka, H., Ikeda, K.: US20016177011 (2001). [94] Morimoto, K., Watanabe, N., Urabe, H., Hirono, M., Yamamiya,
[36] Kim, J.-J., Kim, C.-K., Kwak, S.-Y.: US5593588 (1997). K.: US20056855755 (2005).
[37] Ekiner, O.M., Simmons, J.W.: US20087393389 (2008). [95] Nagakura, K., Matsuo, S.: US2005133509A1 (2005).
[38] Takai, M., Matsumoto, Y., Sekiguchi, K., Kakiuchi, T., Tsuruta, K., [96] Liedloff, H-J., Schmid, E., Hagen, R.H.: US20087348046 (2008).
Shimizu, T.: US20087364660 (2008). [97] Uchida, K., Kikuchi, H., Kashimura, T., Yamashita, T., Yamasaki,
[39] Demakas, J.J., Johnston, B.W.: US2007156145A1 (2007). H.: EP1860134 (2007).
[40] Johnson, D.: US2007265565 (2007). [98] Lovett, B.A., Rosenberg, A. M.: US2007134458A1 (2007).
[41] Shirakashi, Y., Watanabe, T., Asakura, O., Irikura, A., Il, K., [99] Blondel, P., Briffaud, T., Linemann, A., Egret, H., Nogues, P.:
Watanabe, M., Kojima, H., Imai, N.: US2008314402A1 (2008). US20087388048 (2008).
[42] Sugiyama, H., Bando, T., Saito, I.: US20087456294 (2008). [100] Nozaki, M., Kuroe, T.: EP1023397 (2007).
[43] Moriyama, H., Tsukuda, A.: US2006106193 (2006). [101] Nakamura, K., Miyamoto, A.: US20036541559 (2003).
[44] OH, T.-J.: WO2008044851A1 (2008). [102] Fujii, O., Sarukawa, K.: US20036541559 (2008).
[45] Suh, D.-H., Cheng, E.-Y., Rhee, T.-H.: US20006028159 (2000). [103] Bellet, G., Amouroux, N., Montanari, T.: US2009017247A1
[46] Hasegawa, Y., Nagasawa, J.: US2006177244A1 (2006). (2009).
[47] Hsu, R.C., Hsu, H.C.: US2006239624A1 (2006). [104] Harikae, S.: US2006137796 (2006).
[48] Shin, H.H., Nam, M.S., Park, S.H., Ree, M., Lee, S.W.: [105] Westage, W.K., Arumugam, Y.S., Gartland, R.J.: US20097484545
US20067083833 (2006). (2009).
[49] Kwon, S.B., Lee, M.H., Park, S.H., Reznikov, Y., Kurioz, Y., [106] Noguchi, H., Komine, T.: US20016331340 (2001).
Gerus, I.: US20067060332 (2006). [107] Nomoto, K.: US20036544622 (2003).
[50] Oka, H., Matsuoka, H., Kuri, T.: US20067009029 (2006). [108] Liu, Z., Mehta, S., Huang, X., Schiraldi, D.A.: US2006246245
[51] Crowe, C.W., Saito, M.: US2008167404A1 (2008). (2006).
[52] Martens, M.M., Topoulos, G.: US2006293427A1 (2006). [109] Presenz, U., Sutter, M.: US20087442333 (2008).
[53] Kitani, M., Ichikawa, H., Tsukioka, T., Miki, T., Kuramoto, M.: [110] Tsai, M.L., Akkapeddi, M.K.: US20026479160 (2002).
EP1939949 (2008). [111] Akkapeddi, M.K., Socci, E.P., Kraft, T.J.: US20046756444 (2004).
[54] Yamada, T., Nakatani, M.: US5853907 (1998). [112] Bernard, L.G., Clauberg, H., Cyr, M.J., Gilmer, J.W., Owens, J.T.,
[55] Handa, M., Oya, T.: US20036589663 (2003). Stewart, M.E., Turner, S.R., Bagrodia, S., Matayabas, J.C.:
[56] Murayama, S., Wada, M., Matsui, M.: US20016280843 (2001). US20046777479 (2004).
[57] Wada, M., Murayama, S., Matsui, M.: US20026407017 (2002). [113] Maruo, K., Kanda, T., Yamamoto, K.: US20056841651 (2005).
[58] Kurumatani, S., Hiraoka, H., Noda, M., Terao, T., Toyoshima, S., [114] Schulz, D., Holzmuller, A.: US2006127658 (2006).
Kato, Y., Ueno, H.: US20026426310 (2002). [115] Nakamura, K.: US2007160806A1 (2007).
[59] Murayama, S., Matsui, M., Wada, M., Ishihara, S.: [116] Nanba, H.: US2008020218A1 (2008).
US20056838401 (2005). [117] Kohli, A., Forsten, H.H., Wyss, K.H.: US20087456120A1 (2008).
[60] Iwama, M., Takahashi, T.: US20056942757 (2005). [118] Kennedy, III, T.J., Neil, J.T., Binette, M.L., Melanson, D.M.:
[61] Idemura, S., Haraguchi, K.: US20006063862 (2000). US2003078116 (2003).
[62] Miyabo, A.: US20016288145 (2001). [119] Takiue, K., Fujita, H.: EP1985728A1 (2008).
[63] Levit, M.R.: US20006120643 (2000). [120] Elkovitch, M.D., Fishburn, J.R., Ting, S.-P.: US20077182886
[64] Wang, X., Tao, S.: US20036551456 (2003). (2007).
[65] Kawka, D.W., Anderson, D.W., Brown, M.J.: US20087335276 [121] Gottschalk A., Fisch, H., Pipper, G., Weber, M.: US5883186
(2008). (1999).
[66] Bersted, B., Bishop, T.D.: US2005197452A1 (2005). [122] Lapierre, F.: US20036576025 (2003).
[67] Hartzler, J.D.: US20026436236 (2002). [123] Nozaki, M., Koshida, R., Tasaka, T., Ushida, T.: US20046784279
[68] Shinohara, Y., Takahashi, T.: US20036642282 (2003). (2004).
[69] Akatsuka, Y., Moteki, S., Uchida, M., Ishikawa, K.: EP1876873 [124] Ogo, Y., Shiomura, T.: US20036656589 (2003).
(2008). [125] Amimoto, Y., Ogo, Y., Sakka, M.: US20016319986 (2001).
208 Recent Patents on Materials Science 2009, Vol. 2, No. 3 García et al.

[126] Oka, H., Hara, T., Sasaki, S.: US20056846868 (2005). [158] Kosaka, M., Muranaka, Y., Wakatsuru, K.: US20006133406
[127] Montag, R.A., Corbin, G.A., Garrett, D.W.: US20016306951 (2000).
(2001). [159] Liou, G.-S., Hsiao, S.-H., Yang, J.-C.: US5856572 (1999).
[128] Hewel, M.: US2008274355A1 (2008). [160] Phillion, D.P.: US2004092770A1 (2004).
[129] Ebert, M., Furst, R., Felsberger, F.: US20056956081 (2005). [161] Liaw, D.-J., Liaw, B-Y.: US20006087470 (2000).
[130] Rulkens, R., Crombach, R. C. B.: WO2007085406A1 (2007). [162] Liaw, D.-J., Liaw, B-Y.: US5844065 (1998).
[131] Topoulos, G.: US2008070023 A1 (2008). [163] Ishihara, K., Yamamoto, H.: US20036586555 (2003).
[132] Elia, A.E., Renken, A., Mesaros, D.V.: US2008008879A1 (2008). [164] Choi, K.-Y., Suh, D.H., Yi, M.H., Hong, Y.T., Jin, M.Y.:
[133] Uchida, K., Hara, T.: US20056887930 (2005). US5955568 (1999).
[134] Montanari, T., Recoquille, C.: US20056916517 (2005). [165] Choi, K-Y., Lee, J.H., Hong, Y.-T., Jin, M.Y., Choi, K.-S., Park,
[135] Bühler, F.S.: US20036528560 (2003). H.-J.: US20026433184 (2002).
[136] Cheng, P.P.: WO2006020845A3 (2006). [166] Xu, J.J.: US20056914093 (2005).
[137] Takaragi, S., Ohsugi, M., Araki, T., Ohara, T.: US20046787059 [167] Ng, H.: US20026355769 (2002).
(2004). [168] Mallakpour S, Kolahdoozan M. Synthesis and properties of novel
[138] Conley, J.A., Lundblad, L.O., Merriman, E.A.: US20087455750 soluble aromatic polyamides from 5-(2-phthalimidyl-3-methyl-
(2008). butanoylamino)isophthalic acid and aromatic diamines. React Funct
[139] Hikichi, A., Haruta, M., Horiguchi, K.: US20036670408 (2003). Polym 2008; 68(1): 91-96.
[140] Ampuero Auza, J.A., Levit, M.R., Nelson, A.R.: US20077247587 [169] Akcelrud L. Electroluminiscent polymers. Prog Polym Sci 2003;
(2007). 28(6): 875-962.
[141] Auza, J.A.A., Levit, M.R., Nelson, A.R.: US20067015159 (2006). [170] Ghaemy M, Barghamadi M. Fluorene-ring-containing diamine and
[142] Han, I.-S., Lee, J.-Y., Lee, S.-H., Kim, J.-Y., Kwon, S.-Y.: resultant soluble thermally stable polyamides. J Appl Polym Sci
US2008200640A1 (2008). 2008; 110(3): 1730-1738.
[143] Han, I.-S., Lee, J.-Y., Lee, A.-H., Lee, C.-B., Kwon, S.-Y.: [171] Yen HJ, Liou GS. Novel Thermally stable triarylamine-containing
US2008221299A1 (2008). aromatic polyamides bearing anthrylamine chromophores for highly
[144] Han, I.-S., Lee, J.-Y., Kim, J.-Y., Park, T.-H., Kwon, S.-Y.: efficient green-light-emitting materials. J Polym Sci Part A: Polym
US2008227947A1 (2008). Chem 2008; 46(22): 7354-7368.
[145] Willemsen, S., Stuut, H.A.M.: US20087438975 (2008). [172] San-José N, Gómez-Valdemoro A, García FC, et al. Synthesis and
[146] Sugioka, T., Sugiura, M., Hoshida, T., Osako, M., Shimo, T., characterization of novel poly(amide urea)s, materials with
Murase, H., Yamaguchi, T., Yamashita, J.: EP1489152 A3 (2005). outstanding mechanical properties. J Polym Sci Part A Polym Chem
[147] Underwood, G.: EP1414906 (2007). 2007; 45(23): 5398-5407.
[148] Underwood, G.: US2004198891A1 (2004). [173] Yokohama A. Converting step-growth to Chain growth conden-
[149] Underwood, G.: EP1414906 (2007). sation polymerization. Macromolecules 2007; 40(12): 4094-4101.
[150] Yamada, T., Ban, H., Kudo, H.: US20067098273 (2006). [174] Jikei M, Kakimoto MA. Dendritic aromatic polyamides and
[151] Presenz, U., Schmid, S., Hartmann, R., Luck, R.S.: polyimides. J Polym Sci Part A: Polym Chem 2004; 42(6): 1293-
US20056881477 (2005). 1309.
[152] Etchells, III, A.W., Mallon, F.K.: US20067009028 (2006). [175] Wang L, Wang Y, Ren l. Synthesis and characterization of novel
[153] Tsujii, Y., Maruyama, G., Ogawa, K., Takada, Y., Koishi, K., biodegradable aromatic-aliphatic poly(ester amide)s containing
Susuki, K.: US20087381788 (2008). ethylene oxide moieties. J Appl Polym Sci 2008; 109(2): 1310-
[154] Winterling, H., Benisch, C., Hahn, T.: US20087470765 (2008). 1318.
[155] Murakami, H., Omori, S., Wakatsuru, K.: US20006130312 (2000). [176] Gómez-Valdemoro A, Calderón V, San-José N, et al. The
[156] Fowkes, S.W.: US20077160978 (2007). extraction of environmentally polluting cations from aqueous media
[157] Baek, J-B., Tan, L-S.: US20036552195 (2003). with novel polyamides containing cation- and anion-selective host
units. J Polym Sci Part A Polym Chem 2009; 47: 670-681.