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Low pressure and low temperature synthesis of polyamide-6 (PA6) using Na0
as catalyst

Article  in  Materials Letters · December 2014

DOI: 10.1016/j.matlet.2014.08.071

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 Materials Letters 136 (2014) 388–392

Contents lists available at ScienceDirect

Materials Letters
journal homepage: www.elsevier.com/locate/matlet

Low pressure and low temperature synthesis of polyamide-6 (PA6)

using Na0 as catalyst
Juan C. Farias-Aguilar n, Margarita J. Ramírez-Moreno, Lucia Téllez-Jurado,
Heberto Balmori-Ramírez
Depto. de Ing. en Metalurgia y Materiales, Escuela Superior de Ingeniería Química e Industrias Extractivas, IPN, UPALM, Av. Instituto Politécnico Nacional s/n,
CP 07738, México D.F., Mexico

art ic l e i nf o a b s t r a c t

Article history: The synthesis and use of plastic materials in several industrial areas has been increasing rapidly in the
Received 31 July 2014 last century. Among the known plastics, the polyamides have excellent mechanical properties as high
Accepted 14 August 2014 strength and wear resistance. This study reports a novel bath synthesis process to obtain polyamide-6
Available online 21 August 2014
(PA6) from ε-caprolactam using metallic sodium as the catalytic agent in an inert atmosphere of N2.
Keywords: During the synthesis process that was proposed, contrary to conventional industrial processes which
Anionic polymerization involve the use of high pressures, the reaction was carried out at atmospheric pressure. The conversion
ε-Caprolactam degree was
90–95% and the degree of crystallinity was 36%; the mechanical properties like tensile
Mechanical properties strength and Charpy impact obtained were similar to that previously reported in the literature.
& 2014 Elsevier B.V. All rights reserved.

1. Introduction a batch process is performed in the VK pipe at 260 1C, between 14

Polyamide-6 (PA6) has an important role in engineering plas-
tics with several advantages such as good mechanical properties,
resistance to friction, and erosion and chemical resistance to
common solvents such as oils or organic compounds. It can be
used in moderate temperature environments due to its distortion
temperature [1,2].
The polycondensation reaction of bifunctional monomers from
amino acids, dicarboxylic acids and diamines, and the ring-
opening polymerization of lactams are the known processes to
obtain PA6 either by the batch process or continuous process
[3–5]. This material has been obtained by polycondensation
reaction from caprolactam which has a ring structure. The nano-
emulsion particles or high molecular weight polyamides are some
developments on synthesis of PA6 [6]. The use of lactams as
precursor of this material as well as the sodium-lactam salts as
catalyst and isocyanates as initiators has been investigated [7,8].
The caprolactam ring-opening polymerization is used due to the
fast reaction kinetics; the product is easy to clean and the resulting
polymer is crystalline [9]. Anionic polymerization using alkali
metals, strong bases (NaOH), metal alkoxides and organometallic
compounds as catalyzer [10] is the common synthesis to obtain
PA6. The common synthesis of PA by hydrolytic polymerization in
n
Corresponding author. Tel.: þ 52 55 57296000 ext. 54209.
E-mail address: b8240109@gmail.com (J.C. Farias-Aguilar).
and 20 h, and it must be done in a controlled atmosphere of
carbon dioxide (CO2) or nitrogen (N2); the cleaning can take
up to 50 h. Some other processes [10] require the use of
expensive catalysts such as metallic hypophosphites and organic
or inorganic salts, and these materials could produce phosphine
gas. Other processes [10] use aromatic or aliphatic acids as
monomers to obtain PA6 at temperatures up to 320 1C and
pressure up to 3 atm. Most of the processes [11,12] produce PA6
with crystallinity values between 20% and 40%. However, studies
with metallic materials as catalysts at low pressures and at low
temperatures are uncommon.
This paper reports a novel synthesis method of polyamide-6
using Na0 as a catalyst at low pressure and temperature. The
mechanical properties and microstructure of this synthesized PA6
are analyzed.
2. Experimental section
Synthesis: The synthesis of PA6 was carried out in a stainless steel
(304 series) reactor of 4.4 L using ε-caprolactam (C6H11NO, Sigma
Aldrich, purity Z99%) as monomer and Na0 as catalyst (Sigma Aldrich,
purity Z99%), by anionic polymerization. The ε-caprolactam was
dried at 60 1C for 6 h. After that, both the monomer and the catalyst
were added to the reactor and heated up to 124 1C for 15 min,
producing sodium–caprolactam. The molar ratio of ε-caprolactam/
Na0 was 1/0.003. Then, the reactor was heated up to a temperature

http://dx.doi.org/10.1016/j.matlet.2014.08.071
0167-577X/& 2014 Elsevier B.V. All rights reserved.
 J.C. Farias-Aguilar et al. / Materials Letters 136 (2014) 388–392
range of 195–210 1C for 2 h. During the reaction process N2 was
used as the carrier gas to avoid the hydrolytic polymerization process.
The material was dried at 60 1C for 45 min and characterized by
several techniques.
The conversion degree of reaction was calculated using the
following equation:
 
M εcap  M without react
¼ XA ð1Þ
M PA  M without react
where
M ε-Cap is the mass of ε-caprolactam;,
M PA the mass of polyamide obtained; and,
M without reacted: the mass of ε-caprolactam that does not react.
Finally, the obtained material was injected at 85 mm/s at 135 MPa
and 243 1C using a CINCINNATI equipment, VH-250 model.
Characterization: The infrared spectroscopy (FTIR) analysis was
performed in a FTIR equipment (Perkin Elmer) coupled with an
Attenuated Total Reflectance (ATR, Thermo Scientific) system. The
spectra were analyzed from 4000 to 400 cm  1 and 32 scans were
made for each sample.
The differential scanning calorimetry (DSC) analyses were carried
out using a Pressure DSC from Instrument Specialist Incorporated.
The sample was heated from 30 to 500 1C at a rate of 20 1C/min and
cooled to 3 1C under N2 atmosphere. The melting point and crystal-
linity were determined from the following equation [11]:
ΔH f
% Crystallinity ¼  100
ΔH 0f
where ΔH 0f ¼ 190 kJ/kg, is the melting heat of a 100% crystalline
polyamide [11].
The X-ray diffraction was carried out in a D8 Focus by Bruker AXS
using Cu Kα radiation, at 35 kV and 25 mA. Diffraction patterns were
recorded from 101 to 901 (2θ) with a step size of 0.021.
The morphology and microstructure of the polyamide-6 were
observed by scanning electron microscopy (SEM) in a JSM 640 L.V.
and by optical microscope (OM) using a CARL ZEISS equipment.
The samples were polished with silicon carbide sandpaper of
number 1200 and alumina of 1 and 5 μm.
Mechanical test: Tensile testing of the material was carried out
using a DOMER system, CL1999 model, with a capacity of 5 t,
which was used during the tensile tests. The tensile testing speed
was set to be 1.5 mm/s. The dimensions of tensile testing speci-
mens were according to ASTM D638-99 [12].
Charpy impact testing was performed according to ASTM
D6110-04 [13] using a Shimadzu device, 86648 series with a
capacity of 0.8 kgf m. The energy necessary to break the material
was calculated using:
Eabs ¼ mgLð cos β  cos αÞ
where
E abs is the break energy (J);,
m the pendulum mass (Kg);,
L: the pendulum length (m);and
g: the gravity (9.8 m/s²).
3. Results and discussion
Structural, microstructural and thermal characterization: The results
from IR analysis are shown in Fig. 1. The spectrum of ε-caprolactam
389
A)
Transmittance (a.u.)
C=O
1364 cm
3214 cm
-1
2929 cm
-1 1442 cm
1657 cm
3074 cm 964 cm 937 cm
B) 1188 cm
1199 cm
1261 cm
730 cm
2863 cm 1372 cm
685 cm
1417 cm
2933 cm 575 cm
3304 cm
1463 cm
1535 cm
1637 cm
4000 3500 3000 2500 2000 1500 1000 500
Wave number (cm-1)
Fig. 1. FTIR spectrum of the starting material (A) and (B) obtained polyamide-6.
(Fig. 1A) shows bands located at 3214 cm  1 and 1657 cm  1 that
correspond to the stretching vibration of N–H and CQO bonds,
respectively [14] and they are related to typical self-associated
hydrogen bonds formed between CQO and N–H that define the
amide II mode. The bands located between 3500 and 2750 cm  1
correspond to the methyl alkyl group (–CH2–, from cyclic lactam)
related to the bands in the region of 1465–1145 cm  1. The bands at
1486 and 1442 cm  1 correspond to the scissor vibration in the –
CH2– group and the band located at 1417 cm  1 was assigned to the
bending vibrations in the same group. Also, the bands at 1333, 1312,
1289, 1258 and 1196 cm  1 correspond to the amide group bonded
ð2Þ
with the alkyl group (–NH–CH2–). The CQO bond related to lactam
was observed at 1657 cm  1 and confirmed by the bands at 835 and
695 cm  1.
The characteristic spectrum of PA6 is shown in Fig. 1B [15]. It
can be observed that the bands located at 3304 and 1535 cm  1
were assigned to stretching and bending vibration of the hydrogen
bonds in the amide II, respectively. The band at 1637 cm  1
corresponds to the bending vibrations in the same bonds of amide
in mode I. The bands at 685 and 575 cm  1 are assigned to the
torsion in hydrogen bonds of the mode I and mode II of amide,
respectively. Also, the presence of two bands at 1199 and
1188 cm  1 is according to amide mode III. The band of the
carbonyl group (–CO–) is located at
1637 cm  1 and it is over-
lapped with the band of mode I of the amide. However, the band at
3074 cm  1 corresponds to the intramolecular bond between
amide and carbonyl groups (–CONH2). As it was mentioned above,
the OQC–N bond related to the ring of caprolactam was broken
(ring opening) due to the catalyst and the sodium–caprolactam
was formed (R-NH3þ ); this is confirmed since a band is located at
3074 cm  1. In addition, the ring opening is confirmed by the
presence of the band at 1261 cm  1 which corresponds to the
ð3Þ Caliphatic–N bond. The observed bands were located at 2933 and
2863 cm  1 assigned to the vibration of symmetrical and asymme-
trical stretching of –CH2 and –CH3 groups respectively. They were
confirmed due to the presence of the bands at 1463 and
1417 cm  1 assigned to –CH2– (scissors vibration) and the band
at 1372 cm  1 that corresponds to –CH3 group. The band located at
730 cm  1 is related to the presence of the –(CH2)n– chains, where
n Z4. Finally, a crystalline PA6 phase (α) is indicated by the
characteristic bands around 964, 959 and 928 cm  1.
The thermal analyses are shown in Fig. 2. The ε-caprolactam is
thermally stable at low temperatures (Fig. 2A, ○). The thermogram
shows two exothermic peaks at 68.24 1C (ΔHf ¼ 210 kJ/kg) and
110 1C (ΔHd ¼1007.20 kJ/kg) due to the melting and the boiling
points, respectively. The PA6 shows two endothermic peaks
(Fig. 2A, ■) at 223 and 456 1C. The first signal is attributed to the
390 J.C. Farias-Aguilar et al. / Materials Letters 136 (2014) 388–392

Fig. 2. Thermogram of the (A) ε-caprolactam (○) and PA6 (■). (B) Data to calculate crystallinity degree.

absorption of heat required to melt the material (ΔHf ¼58.61 kJ/kg)

and it has a shoulder at 213 1C that corresponds to the melting of
the crystalline portion of the PA6 material; the two peaks are
caused by the polymorphism of the sample. According to some
authors [1], there are two types of crystalline structures in PA6:
pseudo-hexagonal crystallites (γ phase) that melt at 215 1C and a
monoclinic structure (α phase) that melts at 22471.5 1C, as shown
by XRD [16]. Furthermore, there is an endothermic peak located at
456 1C (ΔHd ¼508.80 kJ/kg) attributed to the onset of decomposi-
tion of the material. This result shows that the obtained material
corresponds to the semi-crystalline PA6 with the common melting
temperature ranging from 220 to 230 1C [4].
The degree of crystallinity was determined from the heat of
fusion of the synthesized material relative to that of theoretical
100% crystalline sample of the same material (Eq. (2)). As absolute
100% crystallinity is not obtainable, a calculated or theoretical
value is used. The method used to remove the previous thermal
history from the specimen is by heating it above its melting point.
Due to which, the polymer was heated up to 250 1C at 20 1C/min
and subsequently it was cooled to 3 1C/min (see Fig. 2B). According
to Eq. (2), the crystallinity of the material was 36.01%. The degree
of crystallinity depends on the polymerization temperature, when
it is lower than PA6 melting temperature the crystallinity degree is
higher but the conversion decreases. The contrary happens with
temperatures higher than 220 1C. The temperature affects the
material obtained by anionic polymerization seriously since it
changes between 30% and 50% [9,11,17]. In the synthesis by
hydrolytic polymerization, the crystallinity degree increases up
to 30% [9]. Since polymerization and crystallinity occur simulta-
neously, there is an optimal temperature to reach a high level of
crystallinity in the polymer and therefore higher mechanical
properties can be obtained. Also, an adequate quantity of catalyst
is necessary since the reaction rate is higher; the reactive groups
can be trapped inside growing crystals before they can polymerize
decreasing the conversion; in other words a 100% polymerization
is not achievable [18].
The existence of the crystalline phase in the polyamide-6 was
confirmed by X-ray diffraction (022-0700 JCPDS card) (Fig. 3). The
diffraction pattern shows that two polymorphs of polyamide-6
(α and γ) coexist in the material [9]. These are identified by the
characteristic peaks at 2θ¼21.81, and at 2θ¼111, associated with
the γ phase (pseudo-hexagonal); while phase α (monoclinic) has
the characteristic peaks at 2θ¼20.41 and 23.71.
PA6 usually exhibits these two types of stable crystalline forms,
monoclinic (α) and pseudo-hexagonal (γ) crystal. PA6 molecules
undergoing hydrogen bonding in a parallel chain arrangement
cause the γ phase, whereas hydrogen bonding in anti-parallel chain
Fig. 3. XRD spectrum of the PA6.
arrangement is characteristic of the α form. Besides, it has been
reported that a broad diffraction peak at around 2θ¼ 22.21 represents
the mesomorphicβ form of PA6 [2]. All phases are formed during the
polymerization processes regardless of the raw materials, monomers
and synthesis conditions. γ-Phase is eliminated for the material
exposition in the re-crystallization process. In fact, the main peak in
the DSC analysis at 223 1C and the main peaks from diffraction
patterns at 2θ¼ 20.41 and 23.71, as mentioned above, denote that
the α phase (monoclinic crystal) represents the dominant and stable
crystalline phase in the synthesized PA6.
Morphological characterization: Fig. 4 shows micrographs of the
material surface. The surface looks rough (amorphous polymer) with
scattered circular geometric forms (Fig. 4A and B) attributed to the
spherulites formation [3,4,16,]. These well-defined forms confirm the
semicrystalline nature of the PA6 obtained. At higher magnification,
the morphology of these circles consists of spherical agglomerates
with sizes between 20 and 100 μm. The images obtained by SEM
show particles similar to prisms of smaller sizes, around 10 μm
(Fig. 4C and D).
Tensile and Charpy impact test: The results of the tensile and
Charpy impact strength for the PA6 are shown in Table 1; these
values were comparable with those obtained from literature
[9,19,20].
Commonly, PA6 has an elastic behavior in which the deforma-
tion is less than 0.05% [21]. Also, thermoplastics materials, as
polyamide, exhibit cold drawing, large plastic extension at almost
constant stress during which the molecules are pulled into
alignment with the direction of straining, followed by hardening
 J.C. Farias-Aguilar et al. / Materials Letters 136 (2014) 388–392
Fig. 4. Micrographs of the synthesized polymer by OM (A and B) and SEM (C and D).
Table 1
Mechanical properties of the PA6 obtained.
Property PA6 obtained Common PA [9,11,17,19–22]
Tensile strength (MPa) 37.59 30–100
Young´s modulus (GPa) 0.285 2–3
Charpy impact (kJ/m2) 2.52 1.26–2.52
and fracture when alignment is completed. A high crystallization
degree improves the mechanical properties of this kind of
materials; as it was mentioned there is an optimal temperature
of synthesis that is 4150 1C (crystallization degree of 50%)
[9,11,17]. However, to increase the value obtained in the present
work it is necessary to carry out thermal treatments for the
material as mentioned by Su et al. [23].
The mechanical properties of the obtained PA6 are compared
with those from the literature [9,11,17,19–21] (Table 1). The
maximum tensile strength of polyamide was closer to the inferior
level of common values. The mechanical properties are affected by
the crystallinity degree of the material and by the moisture
during the testing. Udipi et al.[9], Zhi Yong et al.[11] and van
Rijswijk et al. [17] obtained higher mechanical properties because
of the higher degree of crystallinity of their materials. The crystal-
linity degree of the polymer affects the tensile strength and
Young's modulus [24–26], as it can be observed in several types
of polyamides (6, 6/6 and 11) and other polymers (polypropylene)
[24–26]. The mechanical-property/crystallinity-degree ratio is not
linear but mechanical properties have shown a high dependence
with the crystallinity of the materials. In the case of the material
obtained in this work, the crystallinity was
36% which is a value
lower than those reported in some studies. The tensile strength
can be increased by the addition of reinforcement materials
[25,26].
391
4. Conclusions
Polyamide-6 was synthesized via anionic polymerization based
on ε-caprolactam using metallic sodium as catalyst. The material
shows 36% of crystallinity and the result from Charpy impact was
better than the one obtained commonly.
This novel process has the innovation to use atmospheric pressure
and low temperature during the synthesis. In fact, only a flow of N2
was used. This is an important economic factor in the industry,
because the conventional processes employ high pressures which
increase the use of inert gases and therefore it increases the cost.
Acknowledgments
J.C. Farias-Aguilar thanks CONACYT (Grant no. 333343) for
financial support.
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