1714 Communication

Summary: A series of molecular composites of PA 6/PA 66

was synthesized via in situ polymerization. The impact
resistance of PA 6 was improved dramatically by incorporat-
ing a minor amount of PA 66 (2–10 wt.-%), without decreas-
ing the tensile strength. Inserting PA 66 macromolecules at a
molecular level into a PA 6 matrix may interfere with the
arrangement of the hydrogen bonds of PA 6, in turn changing
the crystalline structure and impeding the crystallization of
PA 6.

SEM micrograph of the fractured surface of a PA 6/PA 66

composite containing 10 wt.-% PA 66.

Studies on Molecular Composites of

Polyamide 6/Polyamide 66
Yulin Li,1 Guisheng Yang*2
1
Key Laboratory of Engineering Plastics, Joint Laboratory of Polymer Science and Materials, Institute of Chemistry,
the Chinese Academy of Sciences, Beijing 100080, P. R. China
2
Graduate School of the Chinese Academy of Sciences, Beijing, 100039, P. R. China
Fax: (þ86) 10-62559373; E-mail: ygs@geniuscn.com

Received: June 21, 2004; Revised: August 5, 2004; Accepted: August 18, 2004; DOI: 10.1002/marc.200400262
Keywords: hydrogen bonding; impact resistance; molecular composite; polyamides

Introduction In our laboratory, a new approach for improving the

Polyamide 6 (PA 6) is well known as a high performance
engineering plastic with high strength and good fatigue
resistance as well as wearing durability. Nevertheless its
relatively poor notched impact toughness, especially at low
temperatures, restricts its applications in the aerospace and
auto industries. Many efforts have been made to try and im-
prove the impact resistance of PA 6. For example, reactive
elastomeric compounds have been incorporated,[1–11] such
as amine- or hydroxy-terminated elastomers (which are
usually modified by diisocyanate or blocked by dicapro-
lactam), into e-caprolactam by in situ polymerization to
form composites. Because of the poor miscibility of the
elastomer and the PA 6 matrix, large rubbery domains form,
leading to inferior ultimate properties of the composite.
Moreover, a large amount of elastomeric compound is
usually needed to reach the expected toughness.
toughness of PA 6 has been explored. This new approach
involves using a plastic polyamide, polyamide 66 (PA 66),
instead of elastomers to toughen PA 6. By the in situ anionic
polymerization of e-caprolactam with PA 66 dissolved in it,
molecular composites of PA 6/PA 66 were synthesized. It
was found that a small amount of PA 66 dramatically
improved the toughness and elongation of PA 6/PA 66
composites.
The basic concept of making molecular composites of
polyamide 6 with other polyamides is as follows. If one type
of polyamide can be totally dissolved in e-caprolactam
monomer and a homogeneous transparent solution is ob-
tained, this polyamide is thought to be thermodynamically
miscible with the monomer e-caprolactam. If the poly-
amide/e-caprolactam solution is translucent, the system is
only partially miscible. During ring-opening polymeriza-
tion, since e-caprolactam contains an amide ring, no other

Macromol. Rapid Commun. 2004, 25, 1714–1718 DOI: 10.1002/marc.200400262 ß 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
 Studies on Molecular Composites of Polyamide 6/Polyamide 66
groups would be released so the chemical composition of
PA 6 polymer is almost the same as its monomer. In addi-
tion, the strong hydrogen bonding between polyamide and
the e-caprolactam monomer and between the polyamides
plays an important role, which overcomes the phase sepa-
ration problem caused by the reduction of DSmix after
polymerization. Therefore, it is expected that if a selected
polyamide is miscible with e-caprolactam monomer, it will
also exhibit good miscibility with PA 6, and possibly form a
molecular level composite. Because of the very rapid rate of
anionic polymerization of e-caprolactam at low polymer-
ization temperatures, the amide-interchange between two
polyamides will not occur,[12] so it can be deduced theore-
tically that no random copolyamides will be formed.
Experimental Part
Materials
PA 66 was supplied by Pingdingshan PA 66 Salt Co. Ltd. PA 6
was bought from Guangdong Xinhui Meida Co., Ltd. Commer-
cial grade e-caprolactam was obtained from Nanjing Oriental
Chemical Company. The sodium hydroxide (NaOH) and
toluene 2,4-diisocyanate (TDI) (analysis purity) used in this
communication were purchased from Shanghai Chemical Re-
agents Company and used without further purification.
Preparation of PA 6/PA 66 Molecular Composites
PA 66 was dissolved in melted e-caprolactam monomer at
180 8C under nitrogen. The mixture was exposed to a vacuum
at 170 8C for about 20 min to remove water and then 0.2 wt.-%
of NaOH was added under stirring and exposed to a vacuum for
another 10 min. 0.4 wt.-% of TDI was consequently added with
stirring. The final mixture was then immediately poured into a
mold preheated to 180 8C and polymerized in an oven at 180 8C
for 20 min. After polymerization, the products were cooled to
room temperature and extracted with boiling water to eliminate
the residual monomer. Finally, the PA 6/PA 66 molecular
composites with different PA 66 contents were obtained, which
are denoted as ‘‘PA 6/PA 66’’ below.
Preparation of PA 6/PA 66 Blend Samples
As control samples, co-extruded PA 6/PA 66 composites were
prepared by a f35 twin screw extruder (SHJ-30) at a screw
speed of 240 rpm and barrel temperatures of 230–240–245–
250–250 8C. The pelletized materials were dried and injection
molded into standard testing samples with an injection-mold-
ing machine (SZ-160/80NB). These samples are denoted as
‘‘blend samples’’.
Characterization
The weight-average molecular weight (M w ) of pure PA 6 and
PA 6/PA 66 was determined by intrinsic viscosity measure-
ments ([Z], 97% sulfuric acid) at a concentration of 0.2 g
dl1
Macromol. Rapid Commun. 2004, 25, 1714–1718 www.mrc-journal.de
1715
with a suspended level Ubbelohde viscometer thermostated at
25  0.1 8C. The tensile testing was performed on an Instron
1122 with ASTM D638 and a cross-head speed of 50 mm

min1. The Izod notched impact strength at 23 8C and 40 8C
was measured with an impact testing machine (CSI-137C)
according to ASTM D256.
Scanning electron microscope images were taken from the
impact fractured surfaces of specimens at room temperature,
using a JSM-6360LV SEM.
All the DSC measurements were performed on a Perkin-
Elmer Pyris-1 differential scanning calorimeter (DSC) from
room temperature to 280 8C at a heating rate of 10 8C
min1
under a nitrogen atmosphere, and Tm was determined in the
second scan.
Dynamic mechanical properties of the specimens were
determined on a Rheometric Scientific instrument DMTA IV,
tested under a multiwave dynamic tension mode at a frequency
of 1 Hz and with a temperature ramp of 5 8C
min1.
Wide-angle X-ray diffraction (WAXD) analysis was per-
formed on a Rigaku D/Max-III X-ray diffraction (XRD)
analyzer equipped with a rotating-anode generator system
using CuKa (l ¼ 1.54 Å) radiation at an operating current
of 25 mA and a voltage of 35 kV. The scanning rate was
18 per min.
The films for FT-IR analysis were prepared and examined
according to ref.[13] The thickness ensured the intensity of
the bands was in the range of Beer-Lambert law. The temper-
ature was increased at a speed of 2 8C
min1 and the data were
collected at intervals of 20 8C.
Results and Discussion
M w was estimated by intrinsic viscosity measurements
using Equation (1).[14,15]
M w ¼ 2:81  104 ½Z1:35 ð1Þ
Typical results are given in Table 1. Calculations (see
Table 1) showed that M w decreases with increasing PA 66
content in PA 6/PA 66 composites.
Figure 1A shows the DSC curves of PA 6/PA 66
molecular composites with different PA 66 contents and
the corresponding blend sample. It can be seen that single
melting peaks were observed for all the molecular composi-
tes with different PA 66 contents, while two melting peaks
Table 1. Effect of PA 66 content on M w of PA 6/PA 66
composites.
PA 66 content [Z] M w  104
wt.-% dl
g1
0 4.99 24.65
6 4.40 20.73
12 4.17 19.28
100 1.32 4.09
PA 6 resin 1.20 3.59
ß 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
1716 Y. Li, G. Yang

Figure 1. (A) DSC curves of PA 6/PA 66 composites containing: (a) 0 wt.-% PA 66; (b)
2 wt.-% PA 66; (c) 4 wt.-% PA 66; (d) 6 wt.-% PA 66; (e) 8 wt.-% PA 66; (f) 10 wt.-% PA
66; (g) 12 wt.-% PA66; (h) blend sample with 10 wt.-% PA 66. (B) Loss factor tan d for (1)
PA 6/PA 66 containing 10 wt.-% PA 66 and (2) the corresponding blend sample.

were detected in the blend sample. A lower and narrower former exhibited a similar homogeneous morphology to
peak of tan d was found compared with that of the corres- pure PA 6.
ponding blend sample (see Figure 1B). The lower tan d The mechanical tests (see Table 3) indicate that the Izod
means that chain motion is easier, which may be ascribed to notched impact strength of PA 6/PA 66 was improved dra-
the more disordered hydrogen bonding caused by the matically when a small amount of PA 66, around 4 wt.-%,
incorporation of PA 66. The narrower tan d peak suggests a was incorporated. The impact strength at room temperature
more finely dispersed morphology of PA 66/PA 6. It has may increase 2–3 times compared to that of pure PA 6. The
been reported that PA 6 and PA 66 are miscible in the notched impact strength at 40 8C was also greatly im-
amorphous state.[16] As mentioned above, no random proved. In contrast, the blend samples showed almost no
copolyamide is formed during the present polymerization change in impact strength with PA 66 content. The
process. The added PA 66 is therefore not crystallized but elongation of PA 6/PA 66 increased with increasing PA 66
dispersed in the PA 6 matrix at a molecular level. content until 8 wt.-%. Again no such increase of elongation
As can be seen from Figure 1 and Table 2, with increasing could be observed in the blend samples. At the same time,
PA 66 content in the composites, the melt enthalpy DHf and PA 6/PA 66 retained its good tensile strength until 10 wt.-%
the melting temperatureTm of PA 6 in PA 6/PA 66 decreases, of PA 66 was added.
and the width of Tm becomes broader, indicating that the The WAXD patterns of PA 6/PA 66 in Figure 3 reveal that
crystallinity of PA 6 in PA 6/PA 66 decreases and its cry- the peaks of the a1 crystal form of PA 6 decreased, those of
stallization is more incomplete. In other words, due to their the a2 crystal form increased with increasing PA 66 and the g
good dispersion, PA 66 molecules impede the crystal- crystal form diminished and disappeared when PA 66 con-
lization behavior of PA 6. tent was increased to 10 wt.-%.[11] This suggests that PA 66
Figure 2 shows the SEM morphologies of the impact macromolecules significantly influence the crystalline
fractured surface of composites. The morphology of PA 6/ structure of the PA 6 matrix.[4] We assume that the strong
PA 66 differed totally from that of the blend samples. The interaction between the PA 66 macromolecules and the PA 6
macromolecules results in conformational changes in the
chains, limiting the formation of hydrogen bonded sheets of
a phase, which can be verified by the decrease in the dif-
Table 2. Effect of PA 66 content on DHf and crystallite size (d) of fraction peaks relative to the a2 diffraction peaks with the
PA 6/PA 66 composites.
addition of PA 66. The crystallite size of PA 6/PA 66
PA 66 content DHf d changed slightly with the incorporation of PA 66 (shown in
1
Table 2).
wt.-% J
g nm
Figure 4(I) illustrates the FT-IR spectra of the N–H
0 52.8 13.2 stretching of PA 6 and PA 6/PA 66 in the range 3 100–
2 51.90 14.1 3 500 cm1, which were recorded as a function of incre-
4 51.8 13.2 asing temperature. Although in both cases the N–H
6 47.37 13.5
8 47.53 12.8 stretching peaks shifted towards high frequencies and the
10 42.32 12.2 intensity attenuated, the bandwidths became broader with
12 42.98 12.9 increasing temperature. The rate of increase in the

Macromol. Rapid Commun. 2004, 25, 1714–1718 www.mrc-journal.de ß 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
 Studies on Molecular Composites of Polyamide 6/Polyamide 66 1717

Figure 2. SEM micrographs of fractured surfaces of PA 6/PA 66 composites containing: (a) 0 wt.-%
PA 66; (b) 6 wt.-% PA 66; (c) 10 wt.-% PA 66; (d) blend sample with 10 wt.-% PA 66.

bandwidth with temperature in pure PA 6 was less than that
in PA 6/PA 66 (shown in Figure 4(II)). This difference
reflects the fact that the attenuation and dissociation of
hydrogen bonding with increasing temperature in PA 6/PA
66 are much easier than in PA 6. This is assumed to be due to
the presence of PA 66 macromolecules in the PA 6 matrix
Table 3. Mechanical properties of PA 6/PA 66 with different PA
66 contents.
which interferes with the arranging order of the hydrogen
bonding of PA 6 and leads to more disorder.[13,17,18]
According to the above experimental data, we assume the
following hydrogen-bonded supramolecular association
models of PA 6/PA 66 molecular composites. Because
both pure PA 6 and its molecular composites with PA 66
mainly exist in the a-crystalline form, the primary inter-
molecular interactions occurring in pure PA 6 are hydrogen
bonds between the C O group of one unit and the N–H

PA 66 Elongation Tensile Notched Notched impact

content at break strength impact strength at
strength 40 8C
wt.-% % MPa J
m1 J
m1
0 67 67.4 42 31
2 384 61.2 148 114
4 464 59.7 295 250
6 523 62.0 450 402
8 567 68.5 338 331
10 502 61.3 330 305
12 338 54.0 334 298
0a) 100 63.0 87 11
2a) 88 64.1 87 10
4a) 85 67.3 91 21
6a) 84 68.7 91 12
8a) 25 77.0 79 12
10a) 45 76.5 83 13
12a) 33 77.6 76 14 Figure 3. WAXD intensity profile as a function of PA 66 content:
(a) pure PA 6; (b) PA 6/PA 66 containing 6 wt.-% PA 66; (c) PA 6/
a)
The mechanical properties of the corresponding blend sample. PA 66 containing 10 wt.-% PA 66; (d) pure PA 66.

Macromol. Rapid Commun. 2004, 25, 1714–1718 www.mrc-journal.de ß 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
1718
Figure 4. (I) FT-IR spectra of N–H stretching region of (a) PA 6/PA 66 containing 12 wt.-%
PA 66 and (b) pure PA 6 recorded from 80 8C to 220 8C in the range 2 700–3 600 cm1.
(II) Comparison of the temperature dependence of the width at half-height of the
hydrogen-bonded N–H stretching in the range 3 100–3 500 cm1. (&) pure PA 6; (~)
PA 6/PA66 containing 12 wt.-% PA 66.
group of another. However, in molecular composites of PA
6/PA 66, the addition of PA 66 macromolecules provides
further sites which are capable of forming primary inter-
actions (hydrogen bonds) with the PA 6 N–H or C O
groups. Each time a N–H to C O intermolecular interac-
tion between a PA 6 molecule and a PA 66 molecule is
formed, a corresponding N–H or C O is liberated into free
groups.Accordingly,theoverallnumberofhydrogenbondsin
PA 6/PA 66 molecular composites decreases with increasing
PA 66 content compared with that in pure PA 6, leading to a
more disordered arrangement of hydrogen bonds.
Conclusion
A series of molecular composites of PA 6/PA 66 were
synthesized via in situ polymerization. The impact resis-
tance of PA 6 was improved dramatically without decreas-
ing the tensile strength by incorporating a small amount of
PA 66 (2–10 wt.-%). The specific hydrogen bonding
interaction between PA 66 and PA 6 plays a critical role.
Due to the presence of hydrogen bonding interactions, PA 6/
PA 66 molecular composites could be synthesized success-
fully. Because PA 66 macromolecules were closely
surrounded by PA 6, PA 66 did not crystallize and phase
separate in molecular composites. Otherwise, the crystal-
lization of PA 66 would be a driving force for phase
separation. PA 66 macromolecules inserted into the PA 6
matrix on a molecular level and interfered with the
arranging order of the hydrogen bonding of PA 6, changing
its crystalline structure and reducing its crystallization rate
and crystallinity.
Acknowledgements: This work was supported by the 973
Program of MOST (No. 2003CB615600). The authors gratefully
Macromol. Rapid Commun. 2004, 25, 1714–1718 www.mrc-journal.de
Y. Li, G. Yang
acknowledge Prof. Meiyan Wu and Prof. Dujin Wang for friendly
discussion of the results and the correction of grammar mistakes in
the manuscript.
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