Synthesis of New Optically Active Poly(amide-imide)s
Containing EPICLON and L-Phenylalanine in the Main
Chain by Microwave Irradiation and Classical Heating
Shadpour Mallakpour,* Mohammad Reza Zamanlou
Organic Polymer Chemistry Research Laboratory, College of Chemistry, Isfahan University of Technology, Isfahan,
84156, I.R. Iran
Received 19 June 2003; accepted 5 September 2003
ABSTRACT: EPICLON [3a,4,5,7a-Tetrahydro-7-methyl-5-
(tetrahydro-2,5-dioxo-3-furanyl)-1,3-isobenzofurandione] or
[5-(2,5-dioxotetrahydrofurfuryl)-3-methyl-3-cyclohexyl-1,2-
dicarboxylic acid anhydride] (1) was reacted with l-
phenylalanine (2) in acetic acid, and the resulting amic acid
was refluxed under a Dean-Stark system with benzene,
which produced diacid (3) in high yield. Compound (3) was
converted to the diacid chloride (4) by reaction with oxalyl
chloride in dry carbon tetrachloride. The polycondensation
reaction of this diacid chloride (4) with several aromatic
diamines such as 4,4'-sulfonyldianiline (5a), 4,4'-diaminodi-
phenylmethane (5b), 4,4'-diaminodiphenylether (5c), 1,4-
phenylenediamine (5d), 1,3-phenylenediamine (5e), 2,4-
diaminotoluene (5f), and 1,5-diaminonaphthalene (5g) was
developed by using a domestic microwave oven in the pres-
ence of a small amount of a polar organic medium such as
N-methylpyrrolidone (NMP). The polymerization reactions
were also performed under two different classical heating
methods: low temperature solution polycondensation in the
presence of trimethylsilyl chloride, and high temperature
polymerization. A series of optically active poly(amide-
imide)s with moderate yield and inherent viscosity of 0.14 –
0.22 dL/g were obtained. All of the above polymers were
fully characterized by IR, elemental analyses, and specific
rotation. Some structural characterization and physical
properties of this optically active poly(amide-imide)s are
reported. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91:
3281–3291, 2004
Key words: polyamides; polyimides; microwave irradiation;
l-phenylalanine; viscosity
INTRODUCTION
The energy of microwave radiation is a useful source
for the synthesis of organic compounds. For this pur-
pose, it is necessary to use a polar media to absorb
energy from radiation and translate to the reacting
system. This can create a new method for preparing of
chemical compounds.
1–5
In the field of polymers, the
various types of processing or synthesis, such as
crosslinking of bisamides,
6
the synthesis of poly-
ethers,
7
polyurethanes,
8
imidization of polyamic ac-
ids,
9
and the direct polycondensation of aromatic dia-
mines
10
are from the interesting efforts of using of
microwave radiation. Recently, we have also used
microwave irradiation for the synthesis of organic
compounds as well as macromolecules.
11–16
On the other hand, optically active polymers have
found interesting applications because of their specific
properties. For example these polymers have the abil-
ity of molecular recognition, which cause to use them
as a stationary phase in chromatographic methods for
enantiomeric separations.
17–22
they can also be used as
chiral media for asymmetric synthesis and chiral liq-
uid crystals in ferroelectric and nonlinear optical de-
vices.
23,24
Therefore, the synthesis and application of
optically active polymers have been receiving more
attention. In this area, recently, we have synthesized
optically active polymers by different methods such as
modification of polybutadiene with an optically active
substituted urazole group,
25
Diels-Alder-Ene reac-
tions,
26,27
and the reaction of an optically active mono-
mer with several diamines via solution polymeriza-
tion.
28 –36
In the last case, we use amino acids as a
chiral agent in the backbone of the polymers. Because
the amino acids are naturally occurring compounds,
synthetic polymers based on amino acids are expected
to be nontoxic, biocompatible, and biodegradable. On
the other hand, synthetic polymers containing amino
acid residues in the main chain,
37– 41
or in the side
chain
42
can be used for biomedical applications.
In continuation of our previous works,
28 –36
here, we
wish to report the synthesis and characterization of
new optically active poly(amide-imide)s PAIs contain-
ing EPICLON moieties by using a microwave oven
*Previous name: Shadpour E. Mallakpour.
Correspondence to: S. Mallakpour (MALLAK@CC.IUT.
AC.IR).
Contract grant sponsors: Research Affairs Division Isfa-
han University of Technology (IUT), Isfahan; Center of Ex-
cellency in Chemistry Research (IUT).
Journal of Applied Polymer Science, Vol. 91, 3281–3291 (2004)
© 2004 Wiley Periodicals, Inc.