J Polym Res (2009) 16:681–686
DOI 10.1007/s10965-009-9273-z
ORIGINAL PAPER
Synthesis of polyamides from p-Xylylene glycol
and dinitriles
Moslem Mansour Lakouraj & Masoud Mokhtary
Received: 6 October 2008 / Accepted: 29 January 2009 / Published online: 20 February 2009
# Springer Science + Business Media B.V. 2009
Abstract A series of polyamides were prepared by direct
polyamidation of the p-Xylylene glycol with various
commercially available dinitriles via Ritter reaction. All
the synthesized polyamides showed good solubility in
amide type solvents such as N-methyl-2-pyrrolidone, N,N-
dimethyl acetamide, N,N-dimethyl formamide, and dimeth-
yl sulfoxide. They exhibited inherent viscosities in the
range of 0.25–0.62 dl/g. Elemental analysis, differential
scanning calorimetry, thermogravimetric analysis, infrared
and H1-NMR spectroscopies were used to characterize the
polymers. According to the DSC analysis, the glass
transition temperatures of the polyamides were found to
be 95–174°C. Thermogravimetric analysis indicated that
the polymers show the 10% weight loss temperatures in the
range of 250–350°C.
Keywords Polyamide . Dinitrile . p-Xylylene glycol .
Polycondensation . Ritter reaction
Introduction
Polyamides are high performance materials containing
amide units which exhibit excellent thermal stability and
physical properties [1]. The hydrocarbon segments be-
tween the amide groups can be aliphatic, partially
aromatic, or wholly aromatic. The type of hydrocarbon
segment has effect on the chain flexibility and structural
M. M. Lakouraj (*) : M. Mokhtary
Department of Organic-Polymer Chemistry, Faculty of Chemistry,
Mazandaran University,
Babolsar 47416, Iran
e-mail: Lakouraj@umz.ac.ir
regularity; which this is important for the formation of the
crystalline phase [2–4]. Partial aromatic Polyamides have
been well studied and are of industrial importance.
Linear polyamide of a high enough molecular weight
which to be useful for industrial purpose are generally
difficult to prepare. One of the main encountered difficul-
ties is that very high temperature and critical conditions are
necessary during the polymerization process.
A number of excellent reviews have been written on
polyamides. So far, synthesis of polyamides has been
introduced via ring opening of cyclic amides, direct
amidation of diacids and diamines, and self-condensation
of amino acides. Also, in modified procedures, starting
materials such as diester, diacid chloride, diisocyanate,
silylated amines, and nitriles have been applied to improve
the synthetic methods [5]. However, interfacial polyami-
dation of aliphatic diacid chlorides (ADADS) is unfa-
vorable because of the hydrolysis of acid chloride
groups and due to the early precipitation of low
molecular weight polyamides. In addition, polyconden-
sation with diamines in dry solvents require the addition
of protonacceptor which cause side reactions by elimi-
nation of HCl form ADADS. Furthermore, the use of
silylated aliphatic diamines is also plagued by the same
problem [6, 7]. The Ritter reaction makes possible the
conversion of a group, capable of giving a relatively stable
carbonium ion, to a substituted amide by reaction with a
nitrile in the presence of an acid [8]. Synthesis of some
polyamids by the Ritter reaction that reported previously
includes polyamidation of dinitriles with bis(acetoxy
methyl)duren [9], and reaction of dinitriles with trioxane
[10]. Recently, the application of modified Ritter reaction
in organic transformation [11–16] and in synthesis of N-
tert-butylacrylamide in non-aqueous solvents [17], syn-
thesis of acrylamido acids and copolymerization with
682
Scheme 1 Preparation of model
compound from p-Xylylene H 3C CN+ HOCH 2
glycol and p-tolunitrile
acrylamide [18], synthesis of the acrylamide derivative of
triglycerides and N-poly (alkenel)acrylamide functional
macromonomers have been developed [19, 20]. Therefore,
polyamidation of p-xylylene glycol with dinitriles seemed
to be a promising approach.
The object of the present work is the further develop-
ment of convenient synthesis of polyamide derivatives from
condensation of commercially available p-Xylylene glycol
and dinitriles. Among the reported routes, use of the Ritter
reaction is an attractive method for the synthesis of
polyamides. With this objective, synthesis, characterization
and thermal behavior of various polyamides derived from
p-xylylene glycol and dinitriles were studied. The advan-
tages of this method are to provide a simple, economical
and commercially feasible process to prepare the synthetic
linear polyamides by a convenient polymerization reaction
at relatively low temperature in contradistinction to the high
temperature methods.
Experimental
Materials
All chemicals include dinitriles, p-Xylylene glycol, glacial
acetic acid, p-tolunitrile, boron triflouride etherate, triflour-
omethanesulfonic acid, sulfuric acid 95–97% and solvents
were purchased either from Merck or Fluka chemical
company.
Measurements
Infrared measurements were recorded on a Bruker IFS
48 FT-IR spectrum (Ettling, Germany) using KBr
Fig. 1 1 HNMR (500 MHz)
spectrum of model compound
M.M. Lakouraj, M. Mokhtary
H 2 SO4 / AcOH O O
CH 2 OH H3C N H 2C CH 2 N CH3
r.t H H
(I)
pellets. The 1H-NMR spectra were recorded in DMSO-
d6 solution using a Bruker Avance DPX 500 MHz (GmbH,
Germany). Elemental analyses were performed by a CHN-
O Rapid Heraeus elemental analyzer (Wellesley, MA).
Differential scanning calorimetry (DSC) and thermogravi-
metric analysis (TGA) were recorded on a Stanton Red-
craft STA-780(London, UK). Inherent viscosities were
carried out in a thermostatic bath by means of a viscosity
measuring system Schott Gerate mod. AVS400, equipped
with an ubbelhode viscometer in a concentration of
0.4gdL−1 in NMP at 25°C.
Model compound
Model compound 1 was synthesized from p-Xylylene
glycol and p-tolunitrile. p-Xylylene glycol (5 mmol) and
p-tolunitrile (5 mmol) in glacial acetic acid (5 ml) were
mixed. Then concentrated sulfuric acid (5 ml) was added
dropwise and the mixture stirred at room temperature for
24 h. The obtained amide was isolated by the precipitation
in excess water. Corresponding amide was thoroughly
washed with water and ethanol and dried in vacuum oven
(Scheme 1). Yield 90%; m.p = 230–233°C, FT IR(KBr):
υ = 3282 (NH), 2912(CH aliphatic), 1638 (C=O) cm−1;
1
HNMR (500 MHz, DMSO-d6) δ = 2.35( s, 6 H, Me), 4.4
(d, 4H, CH2), 7.15 (s, 4 H, Ar)7.15–7.8 (d of d, 8 H, Ar),
8.91 (s, 2H, NH) (Fig. 1).
Polyamide synthesis
To a solution of p-Xylylene glycol (5 mmole) and dinitrile
(5 mmol) in glacial acetic acid (5 ml), was added
concentrated sulfuric acid (5 ml) dropwise and the mixture
stirred at room temperature for 24 h. The resulting brown
Synthesis of polyamides from p-Xylylene glycol and dinitriles 683

Table 1 Elemental analysis, Reaction Yields, Inherent viscosities and color of polymers

Polymer Empirical formula Elemental analysis (%) Yield (%) a

ηinh (dL/g) b
Color

N C H

TPN-XG (C16H14N2O2)n Calcd. Found 72.17 5.19 10.52 97 0.6 B

71.7 5.22 9.97
ISPDN-XG (C16H14N2O2)n Calcd. Found 72.17 5.29 10.52 80 0.49 PB
71.9 5.16 10.01
1,2BSDN-XG (C18H18N2O2)n Calcd. Found 73.45 6.16 9.51 96 0.25 PC
72.85 6.2 9.21
1,3BSDN-XG (C18H18N2O2)n Calcd. Found 73.45 6.16 9.51 98 0.26 PB
72.36 6.1 9.11
ADDN-XG (C14H18N2O2)n Calcd. Found 68.27 7.36 11.37 78 0.34 PB
67.71 7.16 11.1
PLMDN-XG (C15H20N2O2)n Calcd. Found 69.2 7.73 10.76 73 0.39 PO
68.3 7.36 10.38
HXDN-XG (C16H22N2O2)n Calcd. Found 70.04 8.08 10.21 75 0.45 C
69.88 7.98 9.98
HPDN-XG (C17H24N2O2)n Calcd. Found 70.80 8.38 9.71 74 0.62 PC
69.8 8.1 9.45
a
Inherent viscosity in NMP (0.4 g/dL) at 25°C
b
B = brown, PB = pale brown, C = cream, PC = pale cream, PO = pale orange

Scheme 2 Preparation of O O
polyamides NC R CN + HOCH2 CH2OH NH R NH CH2 CH2
n
-H2C CH2- -H2C
R= , , ,
CH2-
TPN-XG ISPDN-XG 1,2BSDN-XG 1,3BSDN-XG
(CH2)4 , (CH2)5 , (CH2)6 , (CH2)7
ADDN-XG PLMDN-XG HXDN-XG HPDN-XG

Fig. 2 IR spectrum of
polyamide TPN-XG
684 M.M. Lakouraj, M. Mokhtary

Fig. 3 1 HNMR (500 MHz)

spectrum of polyamide
TPN-XG in DMSO-d6

solution was poured onto crushed ice and the precipitates
were collected by filtration, washed well with cold water
and soxhlet for 4 h in methanol solvent then dried in
vacuum oven.
Results and discussion
The selection of acid is important in the Ritter reaction. We
examined different acids such as triflouroacetic acid, boron
triflouride, triflouromethanesulfonic acid and sulfuric acid
in the presence of acetic acid as a solvent in this reaction. In
the case of triflouroacetic acid, it observed that p-Xylylene
glycol and solid dinitriles don’t have adequate solubility
and polyamidation doesn’t proceed. Boron triflouride is
only suitable for liquid dinitriles due to insolubility of the
solid dinitriles in ethereal solution of boron triflouride. The
best catalyst/solvent system for conducting the polymeriza-
tion is sulfuric acid or triflouro methanesulfuric acid in
acetic acid which permits the convenient preparation of
polyamides at room temperature. This system offers the
advantage of being solvent for both starting materials and
polymers. This procedure can be adapted to a variety of
aromatic and aliphatic dinitriles. Indeed, triflouromethane-
sulfonic acid could be suitable for polyamidation, but
triflouromethane sulfonic acid is extremely stronger and
more expensive acid. Therefore throughout this study, we
selected sulfuric acid as a suitable acid for preparation of
polyamides. The polyamidation reactions were carried out
in the presence of 1:1 (V/V) ratio of sulfuric acid to acetic
acid at room temperature. Table 1, shows the results of
polyamidation of p-Xylylene glycol with dinitriles using
concentrated sulfuric acid in glacial acetic acid. The
polymers were obtained in good to excellent yields within
24 h at room temperature. The yields and solution
viscosities were not affected significantly under prolonged
polymerization time (up to 48 h). It is proposed that the
insitu generated benzylic carbonium apparently reacts with
the nitrile group to form iminium species that can be
transformed to amide by addition of water molecule to this

Table 2 Thermal characteristic

data Polyamide Tg (°C) T10 (°C) T max (°C) Char yield at 550°C (%)

TPN-XG 174 350 375 49

ISPDN-XG 170 335 372 48
Tg: glass transition temperature 1,2BSDN-XG 165 250 400 33
T 1 0 : Temperature for 10% 1,3BSDN-XG 168 275 389 37
weight loss ADDN-XG 102 300 401 36
Tmax: maximum decomposition PLMDN-XG 97 310 350 32
temperature HXDN-XG 99 265 385 26
Char yield: weight of polymer HPDN-XG 95 315 399 27
remained
Synthesis of polyamides from p-Xylylene glycol and dinitriles 685

Fig. 4 TGA curves of

TPN-XG, 1,3BSDN-XG,
HXDN-XG and HPDN-XG

intermediate species. This is supported experimentally by XG polymer shows peaks at about δ: 9.14 (2H, NH amide),
the fact that polyamidation can not be proceed without 8.08–7.29 (CH aromatic, 8H), 4.46 (CH aliphatic 4H)
using a carbonium stabilizing solvent such as acetic acid. (Fig. 3). The yield, inherent viscosity and elemental
When the polymerization of p-Xylylene glycol with analysis of the polyamides are represented in Table 1.
dinitriles was carried out in higher temperature (> 50°C), The inherent viscosity of polyamides was measured in
all polymers were black and insoluble in most organic concentration of 0.4gdL−1 in NMP at 25°C were about
solvent, presumably because of polyalkylation of aromatic 0.25–0.62 dL/g. The resulting polyamides don’t have a very
rings and crosslinking of the resulting oligomers. high molecular weight as is established from solution
Scheme 2 shows the synthetic route used for the viscosities, and indicates moderate molecular weights. In
preparation of linear polyamides. Polymers obtained from the case of polyamides correspond to ortho and meta-
various dinitriles and p-Xylylene glycol were identified by dinitriles (1,2BSDN-XG and 1,3BSDN-XG), the lower
IR, NMR, and elemental analysis. The infrared spectra of viscosity is probably because of intermolecular cyclic
the resulting polymers established corresponding amide amidation, and oligomer formation. These polyamides can
absorptions. As an example, the FT-IR spectrum of TPN- be used in solid form as hot-melt adhesives with particu-
XG polymer (Fig. 2) showed characteristic bands at about larly pronounced adhesion properties, and some of low
3291 (N-H stretching), 2920 (Ar-CH), 1635 (C=O stretch- molecular weight polyamides are widely used as hardener
ing), 1542 (N-H bending) 1419 (C-N stretching) and for epoxy resin [21]. Long et al, [22] suggested that the
1290 cm−1 (C-O stretching). 1H-NMR spectrum of TPN- most desirable polyamides to be blended with PET or PEN
have an average molecular weight of 4,000–7,000 and
Table 3 Solubility of polyamides a inherent viscosity of 0.3–0.6 dl/g. Practically, dropwise
addition of concentrated sulfuric acid to the mixture of p-
b
Polyamide NMP DMSO DMF Solvents m-cresol Xylylene glycol and dinitrile in glacial acetic acid has
DMAc found to be effective to give better yield and higher
TPN-XG ++ ++ + + +
molecular weight.
Depending on the structure of the dinitriles, symme-
ISPDN-XG ++ ++ + + +
try and odd or even number of carbon atoms which
1,2BSDN-XG ++ ++ + + +
affect stiffness or chain flexibility of the polymer
1,3BSDN-XG ++ ++ + + +
backbones, the glass transition temperatures showed in
ADDN-XG ++ ++ + + +
the range of 95–174°C according to the DSC analysis.
PLMDN-XG ++ ++ + + +
The thermal stabilities of polyamides were evaluated by
HXDN-XG ++ ++ + + +
thermogravimetric analysis (TGA) in nitrogen at heating
HPDN-XG ++ ++ + + +
rate of 10°C/min. Thermogravimetric analysis of poly-
a
Solubility: ++, soluble at room temperature; +, soluble in hot solvent mers indicated that the 10% weight loss temperatures
b
Solvents: NMP, N-methyl pyrrolidone; DMF, N,N-dimethylforma- were recorded in the range of 250–350°C and also the
mide; char yields of polymers at 550°C were about 26–49%.
DMAc,N,N-dimethyl acetamide; DMSO, dimethyl sulfoxide The obtained results are summarized in Table 2 and the
686
representative TGA for some samples were shown in
Fig. 4.
The solubility behavior of polyamides was examined in
different solvents. It is found that polymers were readily
soluble in polar aprotic solvents such as N-methyl pyrrolidone
and dimethyl sulfoxide at room temperature (Table 3). In the
case of N,N-dimethylformamide, dimethyl acetamide, and
m-cresol the polymers showed solubility upon heating. There
were no significant differences between solubility behaviors
of different polyamides.
Conclusion
A convenient method utilizing Ritter reaction is applied
for the synthesis of variety of polyamides. This
procedure provides a simple polymerization process for
preparation of moderate molecular weight polyamides
from p-xylylene glycol and dinitriles at room temperature.
Currently we are extending this method for the synthesis
of polyamide derivatives such as poly etheramides and
poly sulfonamides.
Acknowledgments We are grateful to Mazandaran University for
financial assistance of this work.
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