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EUROPEAN
POLYMER
JOURNAL

European Polymer Journal 44 (2008) 12471251

www.elsevier.com/locate/europolj

Antistatic ability of 1-n-tetradecyl-3-methylimidazolium

bromide and its eects on the structure
and properties of polypropylene
Yunsheng Ding *, Haiou Tang, Xiaomin Zhang, Shuying Wu, Renyan Xiong
School of Chemical Engineering, Hefei University of Technology, Hefei 230009, China
Received 9 February 2007; received in revised form 11 December 2007; accepted 17 January 2008
Available online 12 February 2008

Abstract
In this study, 1-n-tetradecyl-3-methylimidazolium bromide ([C14mim]Br), one kind of imidazolium ionic liquid (imi-IL),
was incorporated into polypropylene (PP) via melt blending. The measurement of surface resistance (Rs) and volume resistance (Rv) of neat PP and PP/[C14mim]Br blends indicated that [C14mim]Br had excellent antistatic properties. The PP/
[C14mim]Br blend had the best antistatic ability, when the weight ratio of [C14mim]Br to PP reached 3/100. The surface
resistance of PP/[C14mim]Br decreased from the 7.67  1013 to 1.40  107 X whereas the volume resistance of PP decreased
from 2.67  1014 to 2.60  107 X. Semicrystalline morphology and crystal structure were investigated by polarized optical
microscopy (POM) and X-ray diraction (XRD). The spherulites of PP became smaller with the addition of [C14mim]Br,
implying that [C14mim]Br had a nucleating eect in the PP matrix. The XRD study indicates the crystallization process of
PP was aected by [C14mim]Br, and the crystallinity of PP was thus decreased. Scanning electron microscopy (SEM) studies reveal that [C14mim]Br had good dispersion in PP; thermogravimetric analysis (TGA) shows the addition of
[C14mim]Br remarkably increased the thermal stability of PP even though it is a small molecule.
2008 Elsevier Ltd. All rights reserved.
Keywords: Imidazolium ionic liquid; Polypropylene; Blend; Surface resistance; Volume resistance; Morphology; Thermal properties

1. Introduction
Polyolens, especially polypropylene (PP), are
used in many elds covering packaging materials,
electric appliances, and automobile parts, etc. However, PP is generally low in moisture absorption and
high in electric insulation. Therefore, PP is easily
charged by static electricity. The accumulated elec-

Corresponding author. Tel./fax: +86 551 2901545.

E-mail address: dingys@hfut.edu.cn (Y. Ding).

trostatic charges may generate discharges and even

create the danger of explosions [1,2]. For polyolens, the way of incorporating an antistatic agent
into the polyolen matrix to increase its antistatic
ability is popular under current circumstances [2,3].
Ionic liquids, a kind of molten salts at ambient
temperature, have received a great deal of interests
for their quite unique characteristics such as nonvolatility, non-ammability, high thermal stability
properties, high ion density, and extremely high
ionic conductivity, etc. Moreover, some ionic
liquids have good hydrophile properties and surface

0014-3057/$ - see front matter 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.eurpolymj.2008.01.030

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Y. Ding et al. / European Polymer Journal 44 (2008) 12471251

CH3
XR=C14H29, X=Br
Fig. 1. The molecule structure of 1-n-tetradecyl-3-methylimidazolium bromide.

wettability, so ionic liquids could be used as antistatic agents for polyolens [46].
In our previous work [7], the antistatic properties
of the 1-n-tetradecyl-3-methylimidazolium bromide
([C14mim]Br) and commercial antistatic agents such
as HKD151 and HKD520 have been compared.
The eects of weight ratios on the antistatic property and the mechanical properties of PP have been
studied. Speaking to PP, [C14mim]Br showed better
antistatic ability than the commercial antistatic
agents. The PP/[C14mim]Br blend displayed the best
integrity properties when the weight ratio of PP to
[C14mim]Br is 3/100. In this study, [C14mim]Br,
whose chemical structure is shown in Fig. 1, was
incorporated into PP matrix by melt blending. The
antistatic ability, the PP crystal structures, morphologies and thermal properties of the PP/[C14mim]Br
blend were investigated.
The antistatic persistence of [C14mim]Br, surface
resistance (Rs) and volume resistance (Rv) of PP/
[C14mim]Br blend were also measured before and
after it was scrubbed with distilled water for 50
times in this research.
2. Experiment section
2.1. Materials
PP (Grade Q/SHYZ-251) used for this study was
purchased from Sinopec Yangzi Petrochemical
Company Ltd., China. Antioxidant (Grade 1010)
was supplied by NCM Hersbit Chemical Co., Ltd.
[C14mim]Br was synthesized in our laboratory
according to Ref. [8].

was moved to another compression to mould press

and cooled to room temperature with the pressure
of about 2 MPa in order to get the PP/[C14mim]Br
blend.
2.3. Instruments and methods
Surface resistance (Rs) and volume resistance
(Rv) were tested by the megger (Cany Precision
Instruments Co., Ltd, ZC-36) at ambient temperature, relative humidity (RH) 63%. Fractured surfaces of impact specimens were analyzed using a
scanning electron microscope (SEM, JEOL JSM6700F) to study the dispersion of [C14mim]Br in
the PP matrix. Before the observations, the fractured surface was coated with a thin platinum layer
of about 200 nm thick. A polarized optical microscope (Ningbo Sunny Instrument Co. Ltd., XPB2) equipped with numeral camera automatic exposure was used for monitoring the change of spherulites upon crystallization from the blend melts. The
samples were pressed into a thin lm between two
glass slides heated to melt on the hot stage at about
210 C for 5 min and then crystallized at 140 C
for 2 h. X-ray diraction (XRD) studies were performed on a Rigaku D/max-2500 diractometer
using Cu Ka radiation, with the tube voltage of
40 kV and the tube current of 100 mA. Diraction
measurements were conducted within the 2h angle
of 535, at the scanning rate of 6/min. Thermogravimetric analysis (TGA) was carried out with
PerkinElmer-7 thermal analysis system at the heating rate of 20 C/min under a ow of nitrogen in a
temperature range of 50650 C. Antistatic persistence of [C14mim]Br was tested in the following
way. The sample of PP/[C14mim]Br blend was
immersed into distilled water, and scrubbed the
sample surface with absorbent cotton. After this
process and repeating 50 times, the sample were
exposed to air for drying under the conditions of
ambient temperature, 63% relative humidity (RH)
for 24 h, and then the gures of samples Rs and
Rv were measured.

2.2. Preparation of PP/[C14mim]Br blend

3. Results and discussion
[C14mim]Br was kept dried under vacuum at
80 C for 24 h before use. PP, [C14mim]Br and antioxidant were mixed in a cold twin-roll mill with a
weight ratio of 100/3 for about 5 min, then the
resulting mixtures were compression mounded
under 177 C, 2.5 MPa for 10 min. Finally, the mold

3.1. Antistatic properties of PP/[C14mim]Br blend

Surface resistance and volume resistance of neat
PP, PP/[C14mim]Br blend and PP/[C14mim]Br blend
after scrubbing with water are listed in Table 1.

Y. Ding et al. / European Polymer Journal 44 (2008) 12471251

Table 1
Surface resistance (Rs) and volume resistance (Rv) of samples

Rs/X
Rv/X

PP

PP/[C14mim]Br

PP/[C14mim]Br after
scrubbing

7.67  1013
2.67  1014

1.40  107
2.60  107

4.00  107
1.70  108

Compared to neat PP, both the surface resistance

and volume resistance of PP/[C14mim]Br blend
greatly decrease as shown in Table 1. These data
indicate that PP/[C14mim]Br blend has excellent
antistatic properties (log Rs < 9) [9] and [C14mim]Br
is a good antistatic agent for PP. After scrubbing
with distilled water for 50 times, the Rs and Rv of
PP/[C14mim]Br blend change little, which indicates
the [C14mim]Br has good antistatic persistence to
PP. The good antistatic ability and antistatic persistence of [C14mim]Br to PP are due to the structure
of [C14mim]Br and its compatibility with PP matrix
[10,11].
3.2. Characterization of the [C14mim]Br dispersion
and its eects on the PP structure
3.2.1. PP/[C14mim]Br blend morphology
The dispersion of [C14mim]Br in PP matrix was
investigated by SEM. The impact fracture surface
morphology of PP/[C14mim]Br blend was shown
in Fig. 2.
This SEM image reveals that the impact fractured surface of PP/[C14mim]Br blend exhibits characteristic of a typical brittle surface. As we know,
the fractured surface of neat PP is a kind of brittle
surface, so the impact strength of PP/[C14mim]Br
blend should not be aected apparently by the
incorporation of [C14mim]Br. As the organic salt

Fig. 2. SEM images of impacting fracture surface of PP/

[C14mim]Br blend.

1249

has low molecular weight, the existence of

[C14mim]Br particles in the PP matrix could be the
weak point of such materials, so the impact strength
of PP/[C14mim]Br blend decreased even though
[C14mim]Br particles are uniformly dispersed in PP
matrix (white parts in the micrograph), as shown
in Fig. 2. The nucleating eect of [C14mim]Br particles on PP crystallization would decrease the size of
PP spherulites and increase the impact strength of
PP/[C14mim]Br blend, which we will discuss later
in this paper. In view of two eects of [C14mim]Br
in the PP matrix, the impact strength of PP/
[C14mim]Br blend with the weight ratio of 100/3,
decreased slightly compared with neat PP [7].
3.2.2. Eects of [C14mim]Br on the PP spherulitic
morphology
Polarizing optical microscope (POM) images of
neat PP and PP/[C14mim]Br blend are shown in
Fig. 3a and b, respectively. It can be seen from
Fig. 3a that the neat PP exhibits typical maltesecross pattern, corresponding to the a-phase [12].
The birefringence is apparent in the spherulites.
However, there is no typical maltese-cross pattern
in Fig. 3b, which shows a dierent pattern of
spherulites since [C14mim]Br particles provide the
nucleating sites for the PP spherulites to grow.
Then, a larger number of nucleus lead to the formation of smaller spherulites and broader inter-spherulitic region for they impinge one another before
the growth is completed [12]. The perfect spherulites
of PP can not formed since [C14mim]Br incorporates
into PP matrix. This makes [C14mim]Br move from
the inner to the surface of PP easily just like in the
non-crystallization spaces, so this improves the antistatic property of PP [13]. Moreover, the smaller
spherulites in the PP matrix can improve its
mechanical properties [14]. The tensile strength of
PP/[C14mim]Br blend is a case in point, which
increases when the weight ratio of PP to [C14mim]Br
is 100/3 [7].
3.2.3. X-ray diraction of PP and PP/[C14mim]Br
blend
XRD patterns of neat PP and PP/[C14mim]Br
blend are shown in Fig. 4. From the patterns, it
can be seen that there is a typical a-phase crystal
form existing in neat PP and PP/[C14mim]Br blend.
The peaks have also been marked in Fig. 4. in which
the ve main peaks area of neat PP is broader than
that of PP/[C14mim]Br blend, which indicates the
crystallinity and crystal scale of PP in the blend is

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Y. Ding et al. / European Polymer Journal 44 (2008) 12471251

Fig. 3. Optical micrographs showing the spherulites in (a) neat PP, and (b) PP/[C14mim]Br blend, two samples melt-crystallized at 140 C
(2h).

60000
14.02

Intensity/cps

50000

tilled water and has good antistatic persistence to

PP.

neat PP
PP/imi-IL blend

16.9

18.62

40000

3.3. Thermal stability of PP/[C14mim]Br blend

30000

16.86

20000

18.7
21.18 21.88
20.94 21.8

14.12

10000
0

10

15

20
2 /

25

30

35

Fig. 4. XRD of neat PP and PP/[C14mim]Br blend.

aected by the [C14mim]Br due to its nucleation

eect on the PP crystallization.
This result is in agreement with the result of
POM obtained before. The eect of [C14mim]Br
on the PP crystal structure could make [C14mim]Br
more compatible with PP matrix. Thus, the
[C14mim]Br has super anti-scrubbing ability to dis-

In order to compare the thermal properties of

PP/[C14mim]Br blend and neat PP, they are both
hot-molded under the same conditions to prepare
the samples for TGA testing. TGA curves and their
rst derivatives (DTG) are shown in Fig. 5a and b,
respectively. In Fig. 5a, the result indicates the onset
decomposition temperature (Tonset) of PP/
[C14mim]Br blend is about 384 C, which is almost
the same to the Tonset of neat PP, suggesting that
the thermal stability of PP matrix is not declined
by the incorporation of [C14mim]Br, though the
molecular weight of [C14mim]Br is low. DTG curves
of PP/[C14mim]Br blend and neat PP are presented
in Fig. 5b. Since [C14mim]Br has eects on the PP
structure, the thermal degradation process of PP/

b
Deriv. Weight / (%* C-1)

100

Weight / %

80
PP/imi-IL blend
neat PP

60
40
20

0
PP/imi-IL blend
neat PP

-2

450

100

200

300

400

Temperature / C

500

600

100

200

500

300

400

500

600

Temperature / C

Fig. 5. TGA (a) and DTG (b) curves (N2 atmosphere, 20 C min 1) for neat PP and PP/[C14mim]Br blend.

Y. Ding et al. / European Polymer Journal 44 (2008) 12471251

[C14mim]Br blend and neat PP should be dierent.

In Fig. 5b, this dierence can be seen from their
peak shape and their peak point of the highest
decomposition rate. The DTG curve of PP/
[C14mim]Br blend presents a sharper peak than that
of neat PP, and its maximal weight loss point is
about 485 C, relatively higher than that of neat
PP, whose maximal weight loss point is about
480 C. This result indicates that the decomposition
process of PP/[C14mim]Br blend is slowed down by
the existence of [C14mim]Br in the PP matrix,
though the neat PP and PP/[C14mim]Br have almost
the same Tonset. Results of TGA suggest that the
thermal stability of PP is not decreased by incorporating the [C14mim]Br into it via melting blend, and
the decomposed velocity of PP/[C14mim]Br blend is
less than the counterpart of neat PP.
Moreover, there is only one peak in the DTG
curves of the PP/[C14mim]Br blends indicating a
high compatibility of [C14mim]Br and PP matrix in
the PP/[C14mim]Br blend. The high thermal stability
of [C14mim]Br has also been concluded [15], so the
materials properties should not be weaken by the
decomposition and volatilization of [C14mim]Br in
the processing of PP/[C14mim]Br blend.
4. Conclusions
In this paper, surface resistance and volume resistance of PP/[C14mim]Br blend were tested. Results
showed that the surface resistance of PP/
[C14mim]Br blend drastically decreased from
7.67  1013 to 1.40  107 X while the volume resistance decreased from 2.67  1014 to 2.60  107 X,
indicating its good antistatic properties. SEM of
impact fractured surface studies revealed that the
antistatic agent [C14mim]Br had an excellent dispersion in PP matrix. The role of [C14mim]Br as a
nucleating agent, led to the formation of smaller
spherulites in the PP matrix. And the eects of
[C14mim]Br on the PP crystal structure were conrmed by the POM and XRD studies. TGA results

1251

showed that the Tonset of PP/[C14mim]Br blend

reached 384 C, indicating its good thermal stability
since the PP thermal stability was promoted by
incorporating [C14mim]Br into it. Together with
the eects of [C14mim]Br on the PP structure, antistatic properties and thermal stability, it can be considered as a novel kind of antistatic agent for
polyolens with excellent properties. The application scope of imidizolium ionic liquids can be
extended on the strength of its intrinsical structure
and properties.
Acknowledgements
This study was supported by NSFC (No.
10590355), NSF of Anhui Province (No.
50440905) and Annual Important Scientic Research Items of Anhui Province (No. 06022016).
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