Journal of Wuhan University of Technolotgy-Mater. Sci. Ed.

June 2009 367

DOI 10.1007/s11595-009-3367-7

Synthesis and Characterization of Polyamides
Based on Dimer Acid

WANG Wenzhi, ZHANG Zhifang, XU Meiyun, ZHANG Yonghua
(College of Materials Science and Engineering, South China University of Technology, Guangzhou 510640, China)

Abstract: A series of dimer acid-based polyamides were synthesized by melt -polycondensation of
dimer acid and various aromatic diamines, and were characterized by Fourier transform infrared
spectrum (FT-IR) and nuclear magnetic resonance (
1
H NMR). The physical properties of the
polyamides, such as glass transition temperature, melting temperature, decomposition temperature and
mechanical properties were also investigated. The polyamides intrinsic viscosity ranges from 1.8 dLg
1
to
2.2 dLg
1
, and the melting temperature ranges from 140 to 181 . The glass transition
temperatures, observed from dynamic mechanical analysis, fall in the range of 34.8-48.2 . The
physical and mechanical properties of the resultant polyamides are similar to those of the PA1212. The
heat resistance and mechanical properties of poly (4, 4'-diphenylsulfone dimeramide) (PSD) and
poly(4, 4'-diphenyl dimeramide) (PPDI) are comparable to those of PA1212.
Key words: polyamides; dimer acid; polycondensation; aromatic diamines


1 Introduction

Dimer acids are obtained by the polymerization of
the C
18
-acids such as oleic and linoleic acids, and are
environment-friendly chemical reagent with the
characteristics of low price, non-crystallization, being
biodegradable, soluble in hydrocarbons, and reproducible.
Many polyamides can be prepared by
melt-polycondensation reactions using the dimer acid and
different aromatic diamines as raw materials. The dimer
acid-based polyamides possess many advantages such as
beings soluble in many solvents, biodegradable, flexible,
extensive compatibility with other resins and modifiers.
As a result, these polyamides have attracted much
attention in recent years
[1,2]
. Many formulations and
synthesis techniques of dimer acid-based polyamides can
be found in the previous literatures. For example, Fan and
Deng et al
[3,4]
synthesized a series of polyamides from
different soy-based dimer acids and diamines by the
condensation polymerization reactions, and investigated
the influences of different diamines and amino acids on
the physical and thermal properties of the polyamides.
Cavus
[5]
et al also synthesized a series of polyamides by
condensation polymerization in the absence or presence
of monofunctional reactants, and investigated their
influences. However, these dimer acid-polyamides
usually have some shortcomings such as poor mechanic al
strength, inferior dimensional stability and general
thermal property, which limit the applications in
industrial and other special fields. It is significant and
necessary to develop low-cost and high-performance novel
polyamides. Compar ison with the pure aliphatic segments,
the flexible matrix incorporating aromatic segments can
improve mechanical strength and thermal stability
[6,7]
,
attributing to the rigid segmental structure and related
crystal morphology. Thus, the study of dimer acid-based
polyamides with aromatic segments is significant not only
for scientific research, but also for expanding the
commercial applications of these polymers.
In this work, we presented a series of dimer
acid-based polyamides, synthesized using dimer acid and
aromatic diamines of 4, 4'-diaminodiphenyl methane, 4,
4'-diaminodiphenyl ether, 1, 4-diaminobenzene, 4,
4'-diaminodiphenyl and 4, 4'-diaminodiphenyl sulphone.
The resultant polyamides were characterized by Fourier
transform infrared spectrum (FT-IR), nuclear magnetic
resonance (
1
H NMR), thermal analysis, mechanical
property, and dynamic mechanical analysis (DMA).

2 Experimental

2.1 Materials
Dimer acid, supplied by the Yichun Yuanda Chemical
Co. Ltd (China) , is yellowish transparent liquid, with the

(Received: October 15, 2008; Accepted: March 3, 2009)
WANG Wenzhi( ): Ph D; E-mail: wwzscut@gmail.com
*Corresponding author: ZHANG Yonghua( ): Prof.; Ph D; E-mail:
pazhyhua@scut.edu.cn

Vol.24 No.3 WANG Wenzhi et al: Synthesis and Characterization of 368
composition as following: 99%-99.5% dimer, monomer
0.2%, 0.1%-0.3% trimer. 4, 4'-diamino-diphenyl
methane (MD), 4, 4'-diaminodiphenyl ether (ED),
p-phenylene diamine (PD), 4, 4'-diaminodiphenyl(PDI)
and 4, 4'-diaminodiphenyl sulfone (SD) were commercial
grade and purchased from by Shanghai Chemical Co. Ltd
(China). All of the materials mentioned were purified before use.
2.2 Synthesis
Poly(1, 4-phenylene dimeramide) (PPD) was
synthesized as follows (Scheme 1). First, PD (108.2 g, 1
mol) was dissolved in 100 mL water at 70 . Then the
solution was added slowly into 100 mL mixture of
ethanol and terephthalic acid (560.0 g, 1.0 mol) with
vigorous stirring. After stirring the mixture solution for
120 min at 70-75 , the PPD salt solution yielded. The
PPD salt solution was added into an autoclave with a
slight excess of diamine ( 1%) in order to compensate
any possible loss during the polymerization. The
autoclave was filled with carbon dioxide at room
temperature and then heated to 220 , meanwhile, the
pressure was increased to 2.5 MPa. After 2 h, the pressure
was gradually decreased to atmospheric pressure in 2 h
and the reaction temperature of the autoclave was
increased to 265 . After another 2 h under these conditions,
the autoclave was evacuated to 40 Pa and the reaction
temperature was increased to 270 , and kept for 1 h, the
high molecular weight of PPD was obtained (484.4 g, 91
%).
Poly(4, 4'-diphenylmethane dimeramide) (PMD),
poly (4, 4'-diphenylsulfone dimeramide) (PSD), poly(4,
4'-diphenylether dimeramide) (PED) and poly(4,
4'-diphenyl dimeramide) (PPDI) were prepared by the
similar procedures except for using 4, 4'-diamino-diphenyl
methane, 4, 4'-diaminodiphenyl ether , 4, 4'-diaminodiphenyl
and 4, 4'-diaminodiphenyl sulfone to instead of
p-phenylene diamine, respectively.












Polyamide salts were prepared beforehand in order
to maintain the accurately equal reaction ratio of the
diacid and the diamine. At the early stages of the
polycondensation, high vapor pressure was applied to
reduce the diamine loss. Furthermore, a slightly
excessive diamine was added to compensate any loss. In the
last step of polycondensation, the molecular weight of
polyamides increased with the autoclave being evacuated to
40 Pa. Finally, the polyamides with high intrinsic viscosity
wereobtained.
2.3 Characterization
The intrinsic viscosities in concentrated DMF of the
polyamides were investigated in an Ubbelohde
viscometer at 25 0.1 . The FT-IR spectra were
performed on a NICOLET 460 spectrometer using the
melting pressed-disc technique.
1
H NMR spectra were
recorded with a Bruker DPX-400 (400 MHz), using
deuterated trifluoroacetic acid as solvents and
tetramethylsilane (TMS) as an internal reference.
Thermal analysis (DSC-TG) was carried out in a
nitrogen stream using a NETSCH 204 calorimeter with a
heating rate of 10 /min. DMA was performed on a
NETZSCH DMA-242 apparatus operating in tensile
mode at a frequency of 2 Hz in the temperature range of
160 to 100 with a heat rate of 3 /min.
Mechanical properties were investigated by a Universal
testing machine (CMT5104) with a crosshead speed
of 50 mm/min and a gauge length of 50 mm.

3 Results and Discussion

3.1 Infrared spectra
FT-IR spectra of the polyamides are shown in Fig.1.
All the characteristic absorptions of amide groups and
methene segments of polyamide are listed as follows:
3 293-3 308 cm
1
(hydrogen-bonded and N H
stretching vibration), 2 916-2 930 cm
1
(NH in-plane
bending vibration), 1 643-1 659 cm
1
(amide I, C O
stretching vibration), 1 506-1 526 cm
1
(amide II, CN
stretching and CONH bending vibration), 1089-1 105
cm
1
(amide IV, CCO stretching vibration), 719-728 cm
1

(CH
2
wagging).














Scheme 1 Synthesis of the polyamides
Fig.1 FT-IR spectra of the polyamides
Journal of Wuhan University of Technolotgy-Mater. Sci. Ed. June 2009 369

3.2
1
H NMR analysis
Fig.2 presents the
1
H NMR spectra of the
polyamides in deuterated trifluoroacetic acid. The
chemical shifts in the range at 7.0-8.4 ppm is attributed to
the aromatic protons (position 1, 2, 3). The chemical
shifts at 2.6-2.9 ppm originate from the protons at the
position 4 while that at 1.8- 2.0 ppm come from the
protons at the position 5. The peaks at 1.2-1.6 ppm
belong to the protons of the aliphatic chains (position 6).
The peaks at 2.4-2.5 ppm are attributed to the protons at
the position 7. The peaks at 4.0-4.3 ppm belong to the
protons at the position 8. The chemical shifts at 0.8-1.0
ppm originate from the protons at the position 9. The
peaks at 11.7 ppm are attributed to trifluoroacetic acid.
FT-IR and
1
H NMR results indicate that this synthetic
method is very effective to synthesize the desired
products.

































3.3 Thermal behavior
The DSC curves of the polyamides are shown in Fig.3.
The melting temperatures (T
m
) of PPD, PMD, PED, PSD and
PPDI increase from140 to181 in turn with the
increasing rigid of aromatic diamines, and are higher than
those of dimer acid-based aliphatic polyamides. PPD has the
lowest T
m
at 140 and PPDI has the highest T
m
at 181 .
The thermo gravimetric (TG) curves of the
polyamides are shown in Fig.4. All the polyamides begin
decomposition at about 420 , with the framework
collapses temperatures (T
d
) at about 486 , which are
higher than those of dimer acid-based aliphatic polyamides.
The result suggests that the thermal stability of the
polyamides have been improved by incorporating
phenylated linkage into the polymeric backbone. The
thermal property data of the polyamides in this work are
listed in Table 1.












Table 1 Thermal properties of the polyamides
Item PPD PED PMD PSD PPDI
T
m
/ 140 148 159 177 181
T
g
/ 34.8 36.3 40.2 43.5 48.2
T
d
/ 417 416 421 419 428
3.4 Solubility of the polyamides
The solubility of the polyamides was tested with
different organic solvents which are shown in Table 2.
The resultant polyamides are soluble in dimethyl
sulfoxide (DMSO), N,N'-dimethylformamide (DMF),
acetone chloroform, carbon tetrachloride, benzene,
toluene, tetrahydrofuran (THF), concentrated sulfuric
acid and trifluoroacetic acid (TFA) at room temperature,
but insoluble in m-cresol, acetone and benzene. The results
show that the resultant polyamides have favorable
solubility.
Table 2 Solubility of the polyamides
*

PPD PMD PSD PED PPDI
DMF
THF
DMSO
TFA
Sulfuric acid
m-Cresol
Acetone
Chloroform
Benzene
Fig.4 TG curves of the polyamides
Fig.2
1
H NMR spectras of the polyamides
Fig.3 DSC curves of the polyamides
Vol.24 No.3 WANG Wenzhi et al: Synthesis and Characterization of 370
Chlorobenzene
Toluene
Methanol
*The symbols of indicating soluble at room temperature
and indicatinginsoluble.

3.5 Dynamic mechanical analysis
DMA curves of the polyamides are shown in Fig.5.
Two obvious transition behaviors can be observed, and
are defined as , and relaxation, respectively. It is
well known that the glass transition temperature (T
g
) of
polyamide can be determined by relaxation, since it
is usually related to the segment movements in the
noncrystalline area
[8]
. relaxation reflects the
co-moving of amido and methenes, and reflects the
resultant polyamides exhibit fine low-temperature
mechanical properties. The temperatures of relaxation
of PPDI, PSD, PMD, PED and PPD are 49.8 , 43.2 ,
38.6 , 36.5 and 34.6 , the temperatures of ?
relaxation are 108.5 , 111.8 , 117.8 , 122.4
and 126.3 . The and ? relaxation temperatures
increase with the increasing rigid of aromatic diamines.
Meanwhile, ? relaxations in low temperature area also
indicate that the polymers have excellent low temperature
toughness.
3.6 Mechanical properties and water-absorbing of
the polyamides
Dry and standard specimens of the polyamides by
injection-moulding were prepared and their
water-absorbing and mechanical properties were
measured. From Table 3, it can be observed that the
tensile strength (above 40 MPa) and bending modulus
(above 1.2 GPa) of the polyamides are almost the same as
that of PA1212 at room temperature
[8]
. Meanwhile, they
have good toughness and low water-absorbing because
that a long, flexible aliphatic linkage containing a side
group itself are incorporated in the main chain of
aromatic polymer, and the low water-absorbing is
conducive to maintain dimensional and mechanical
stability of products.
Table 3 Physical and mechanical properties of the polyamides
Item PPD PED PMD PSD PPDI
Density /(gcm
3
) 1.09 1.10 1.08 1.12 1.10
Intrinsic viscosity/(dLg
1
) 2.1 1.9 2.2 1.8 1.9
Water-absorbing /% 0.13 0.15 0.14 0.16 0.15
Tensile strength /MPa 42 41 45 46 46
Bending modulus /GPa 1.2 1.3 1.1 1.0 1.2
Impact strength /(kJm
2
) 15.2 15.8 16.3 14.9 13.8

4 Conclusions

a) A series of dimer acid-based polyamides of PPD,
PMD, PED, PSD and PPDI with high intrinsic viscosity
have been synthesized by salt forming and
melt-polycondensation reactions using dimer acid and
different aromatic diamines.
b) With the rigid aromatic diamines being
introduced in the polyamides skeletons, the heat
resistance and mechanical properties are gradually
increased. The heat resistance and mechanical property
of PPDI are superior to those of other polyamides. The
physical properties of the polyamides were comparable to
those of PA1212, and the mechanical properties of PSD
and PPDI are similar to those of PA1212.
c) The resultant dimer acid-based polyamides have
many advantages compared to PA1212 such as the
convenient raw materials, low price, low temperature
toughness, better process ability and favorable solubility.

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