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Highly efficient FeCl3 doped Mg(OEt)2/TiCl4-based

Ziegler–Natta catalysts for ethylene polymerization
a a a b
Reza Bazvand , Naeimeh Bahri-Laleh , Mehdi Nekoomanesh & Hossein Abedini
a
Polymerization Engineering Department, Iran Polymer and Petrochemical Institute (IPPI),
P.O. Box 14965/115, Tehran, Iran
b
Process, Modeling and Control Department, Iran Polymer & Petrochemical Institute, P.O.
Box 14965/115, Tehran, Iran
Published online: 11 Jun 2015.

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To cite this article: Reza Bazvand, Naeimeh Bahri-Laleh, Mehdi Nekoomanesh & Hossein Abedini (2015): Highly efficient
FeCl3 doped Mg(OEt)2/TiCl4-based Ziegler–Natta catalysts for ethylene polymerization, Designed Monomers and Polymers,
DOI: 10.1080/15685551.2015.1041089

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 Designed Monomers and Polymers, 2015
http://dx.doi.org/10.1080/15685551.2015.1041089

Highly efficient FeCl3 doped Mg(OEt)2/TiCl4-based Ziegler–Natta catalysts for ethylene

polymerization
Reza Bazvanda, Naeimeh Bahri-Laleha*, Mehdi Nekoomanesha* and Hossein Abedinib
a
Polymerization Engineering Department, Iran Polymer and Petrochemical Institute (IPPI), P.O. Box 14965/115, Tehran, Iran;
b
Process, Modeling and Control Department, Iran Polymer & Petrochemical Institute, P.O. Box 14965/115, Tehran, Iran
(Received 31 January 2015; accepted 12 April 2015)

Seven Mg(OEt)2/FeCl3/SiCl4/TiCl4 type procatalysts supported on Mg(OEt)2/FeCl3 mixtures were prepared in order to
unravel effect of Fe doping on the catalytic performance in ethylene polymerization. In polymerization experiments, the
catalyst based on a support containing an optimum doping amount of 10 wt.% of FeCl3, i.e. C-F10-Si, exhibited an
activity 2.4 times greater than that shown by the reference catalyst, C-M. The MW and bulk density of the produced
polymers were increased, while the wax amount decreased using doped catalysts. In the next step, the copolymerization
of ethylene with 1-hexene was carried out using C-M as reference and C-Fe10-Si as the most efficient procatalysts. In
copolymerization experiments, C-Fe10-Si exhibited much higher activity and comonomer incorporation in comparison
Downloaded by [FU Berlin] at 00:49 08 July 2015

with reference catalyst. Finally, to shed light on possible interaction of TiCl4 with doped and undoped catalysts, as well
as their efficiency in ethylene polymerization, molecular simulation was performed. Energy results revealed that the
doping does not alter significantly the capability of the Ti to insert ethylene monomer.
Keywords: doping; Ziegler–Natta; polyethylene; DFT calculations; metal halide

1. Introduction tive way to improve their catalytic performance in α-ole-

The use of supports to improve the activity of Ziegler–
Natta (ZN) catalysts has been reported since the early
60s.[1–3] Discovery of active MgC12 as an effective
support for the fixation of titanium tetrachloride opened
a new period in the field of ZN catalysts, both from the
industrial and the scientific viewpoints. Because the use
of MgC12 as a support drastically enhanced the catalyst
activity, a great deal of attention has been focused on the
development of various effective supports, such as inor-
ganic compounds.[4,5]
Nowadays, as two kinds of major industrial materials
of the carrier, MgCl2·nROH and magnesium ethoxide,
Mg(OEt)2, are widely known.[6,7] Although, Mg(OEt)2
has a morphological subject regarding roundness and
particle size distribution as compared with MgCl2·nROH,
the catalyst made by Mg(OEt)2 shows a higher activ-
ity.[8,9]
Industrial catalysts precursors containing magnesium
compounds such as MgCl2 or Mg(OEt)2 in conjunction
with TiCl3 or TiCl4 showed great performance in olefin
polymerization; however, still there are lots of modifica-
tions of ZN catalysts varying in the way of preparation
of the support [10–14] and differences in the active
component compound structure and the presence of vari-
ous modifying additives.[15–18] Lately, investigations
have shown that doping a suitable amount of Lewis
acids in MgCl2 or Mg(OEt)2 supports would be an effec-
fin polymerization. The mostly used doping agents were
based on different metal halides such as MnCl2,[2]
ZnCl2,[3] NaCl,[4] AlCl3 [5,6,19], and the mixture of
metal halide with metalloids like ZnCl2–SiCl4 sys-
tem.[7,8] These agents not only can have notable effect
on catalyst activity but also have the ability to change
catalyst efficiency toward higher α-olefins in LLDPE
production as well as stereo-regularity of final polymer
in propylene polymerization. Furthermore, it was
reported that by doping the MgCl2 support with another
metal halide that would go into the crystal lattice and
cause disorder in it, a disturbance in the setup of active
sites is created which leads into the variety in the nature
of the active sites and a corresponding variety of chain
lengths in the produced polyolefin material.[20,21]
In the present work, we focused on the modification
of Mg(OEt)2/TiCl4 type ZN catalyst using FeCl3 as sup-
port doping agent and SiCl4 as catalyst modifier in order
to expand our knowledge on this important class of ole-
fin polymerization catalysts. To this end, we have pre-
pared seven types of catalysts, using SiCl4 in a constant
content and FeCl3 with different amounts. Then, we
investigated their efficiency toward catalytic activity in
ethylene polymerization and ethylene/1-hexene copoly-
merization as well as some properties of the polymers
obtained thereof. In some cases, to shed light into the
possible interaction of FeCl3 doped supports with TiCl4

*Corresponding authors. Email: n.bahri@ippi.ac.ir (N. Bahri-Laleh); m.nekoomanesh@ipp.ac.ir (M. Nekoomanesh)

© 2015 Taylor & Francis

 2 R. Bazvand et al.
and also their efficiency in ethylene polymerization, DFT
simulation has been performed.
2. Experimental
2.1. Materials
Polymerization grade ethylene with high purity was
obtained from Arak Petrochemical Co. (Arak, Iran) and
was purified by passing through columns of activated
BX and 4 Å molecular sieves. Mg(OEt)2, THF, FeCl3,
SiCl4, potassium hydroxide, and titanium tetrachloride
(99%) were purchased from Merck (Darmstadt, Ger-
many). Toluene and n-hexane were supplied by Bandar
Imam Petrochemical Co. (Mahshahr, Iran), distilled over
calcium hydride, and stored over 13X and 4 Å type acti-
vated molecular sieves and sodium wire. Triethylalu-
minum (TEA) and 1-hexene of 93% purity were
purchased from Aldrich Chemical Co. (Munich, Ger-
many). Nitrogen gas of 99.99% purity was supplied from
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Roham Co. (Tehran, Iran), then purified and dried by
passage through KOH, activated silica gel and 4 Å
molecular sieve columns.
2.2. Preparation of catalysts
2.2.1. Support
The Mg(OEt)2/FeCl3 supports were prepared by mixing
a blend of powdered Mg(OEt)2 and FeCl3 (total weight
of the support was 10.0 g) in 80 mL of THF under rapid
stirring for 8 h under strictly inert atmosphere at 63 °C.
After standing for 1 h, the supernatant liquid was
removed at room temperature by settling, and the pre-
pared support was dried under N2 atmosphere at
P = atmospheric pressure and T = 60 °C within 3 h.
2.2.2. Catalyst
After support synthesis, preparation of the catalysts was
accomplished according to a procedure at Ref. [22].
2.2.2.1. Catalyst M. Two grams of magnesium ethoxide
and 80 mL toluene were sequentially added into a reac-
tor. After stirring for 30 min at 50 °C at which the mix-
ture formed a homogeneous solution, the temperature
was raised to 80 °C. Then, 4 mL TiCl4 was added to the
solution at 80 °C. After 2 h, the liquid phase was
removed, and the solid residue was washed twice with
100 mL of toluene. Then, a mixture of toluene (100 mL)
and TiCl4 (4 mL) was added. The temperature was raised
to 120 °C, and the mixture was stirred for another 2 h.
The product was washed twice with 100 mL toluene and
4 times with n-hexane to remove unreacted TiCl4. The
final catalyst was dried at 70 °C, under a flow of N2
atmosphere in 1 h.
2.2.2.2. Catalyst M-Fn. The Mg(OEt)2/FeCl3 mixed
support and 80 mL of toluene treated with molecular
sieve were successively added into a reactor. The other
steps were the same as those for preparing catalyst M.
2.2.2.3. Catalyst M-Fn–Si. The Mg(OEt)2/FeCl3 mixed
support and 80 mL of toluene were successively added
into a reactor. After stirring for 30 min at 50 °C, 0.2 mL
SiCl4 was added to the solution and stirred for 1 h. The
other steps were the same as those for preparing catalyst
M-Fn.
2.3. Polymerization of ethylene and copolymerization
of ethylene/1-hexene
Ethylene slurry polymerization was performed in a 1-L
Buchi stainless steel reactor equipped with a mechanical
stirrer (Buchi bmd 300, Switzerland). Before each poly-
merization experiment, reactor was purged with nitrogen
gas at 100 °C for 1.5 h to eliminate moisture and oxy-
gen. After running out of all moisture and air by nitro-
gen, 500 mL of hexane was added. After 5 min, a
required amount of TEAL (Al/Ti = 180) and 5 mg of
catalyst were added using syringes. The reactor was
heated up to 80–85 °C, and then ethylene was fed to
maintain a reactor pressure of 5 bar for 1 h. After the
polymerization, reaction was terminated by venting the
reactor. The resulting polymer was filtered off and dried
in oven at 70 °C for 12 h.
The copolymerization reactions were carried out in
the same condition of ethylene polymerization, with this
difference that 1-hexene comonomers was injected to the
reactor after loading of catalyst.
2.4. Characterization
Crystal structure of the supports was determined by
X-ray diffraction (XRD) on a Siemens D-5000 X-ray
diffractometer (USA) operating at 40 kV and 25 mA with
a copper target (λ = 1.54 Å) and at a scanning rate of
3° min−1. The morphologies of the catalysts and EDX
maps were observed by scanning electron microscopy
(SEM model S-3000 N, Hitachi, Japan) after coating
with a gold sputter coating machine (model E-1010,
Hitachi, Japan). The specific surface area of the catalysts
was determined by nitrogen physisorption method. The
single-point specific surface area of the catalysts was per-
formed on Micrometrics Chemisorb 2750 (USA) at
77 K. Prior to the measurement, the catalyst sample was
added into a tube under N2 atmosphere. For determina-
tion of Ti content, after sample digestion in H2SO4, Ti
was oxidized with H2O2 and analyzed by UV–visible
spectrophotometer (λ = 410 nm) in a Shimadzu spec-
trophotometer model 6800, USA.
 Designed Monomers and Polymers
The molecular masses and their distributions were
determined through high temperature gel permeation
chromatography (Waters GPCV 150+, USA), using
1,2,4-trichlorobenzene as the eluent at 140 °C.
The wax amount (the content of soluble part of the
produced polymers) was determined through soxhlet
extraction for 24 h with hexane solvent. The DSC tests
were performed on a DSC Q 1000 of TA (USA), with
samples of about 5 mg sealed in aluminum pans, under
nitrogen atmosphere in a temperature range between 30
and 180 °C, at a heating rate of 10 °C/min. Melting tem-
perature (Tm) and degree of crystallinity (Xc) were
reported from the first heating scan. The degree of crys-
tallinity was calculated via the total enthalpy method,
according to the following equation:
DHm
Xc ¼
DHmþ
Downloaded by [FU Berlin] at 00:49 08 July 2015
where Xc is the degree of crystallinity, ΔHm is the speci-
fic enthalpy of melting, and DHmþ is the specific melting
enthalpy for 100% crystalline PE. We used a DHmþ value
of 288 J/g.[22]
Comonomer content was measured according to
Montell test method, MTM 15984E. This method is
based on a standard test method, ASTM D 2238 – 68,
for absorbance of polyethylene due to methyl groups at
1378 cm−1.[23] The sensitivity of the method is approxi-
mately 0.2 wt.% for 1-hexene content.
Figure 1. Model precatalysts used in molecular simulation studies: (a) Mg3–Ti4, (b) Mg2Fe–Ti4, and (c) Fe3–Ti4.
3
2.5. Computational details
To model the mixed support structure, we considered
three model systems: Mg3–Ti4, Mg2Fe–Ti4, and Fe3–
Ti4, see Figure 1, for labels. These systems mainly differ
for the numbers of Fe atoms involved in the support
structure. In particular, Mg3–Ti4 system can be consid-
ered as a good representative model to study TiCl4
adsorption on the (110)-MgCl2 lateral cut. Because of
the higher acidity of the 110-lateral cut, the absorption
of TiCl4 into this face is more probable than that in 104-
lateral cut, and therefore, there is growing evidence that
the real active Ti species could have a similar environ-
ment.[1,24,25] DFT calculations were performed with
the Gaussian 09 package [26] using the BP86 level of
theory.[27] In all cases, the electronic configuration of
the molecular systems was described with the standard
split valence basis set with a polarization function of
Ahlrichs and coworkers for H, C, Mg, and Cl (SVP key-
word in Gaussian 09).[28] For Ti and Fe, we used the
small-core, quasi-relativistic Stuttgart/Dresden effective
core potential, with an associated valence basis set (SDD
keywords in Gaussian 09).[29] To study the effect of
computational level on the obtained data, some test cal-
culations in Table 4 were performed with the HGGA
PBEh1PBE functional [30] using triple- ζ valence TZVP
basis set.[28]
In case of Mg3–Ti(IV), the singlet, and for Mg3–Ti
(III) and Mg9–Ti(III) species, the doublet electronic
states were used. Differently, for Mg2Fe–Ti(III), Mg8Fe–
 4 R. Bazvand et al.
Ti(III), and Fe3–Ti(III) species, the quartet, and for Fe3–
Ti(IV), the nonet electronic states were favored, since Fe
usually is in high spin mode and the spins of various Fe
atoms in cluster mode are coupled in different ways.
Characterization of the located stationary points as
minima or transition state (TS) was performed by fre-
quency calculations. Total energies and optimized
geometries are provided in Supplemental data.
3. Results and discussion
3.1. Support and catalyst preparation results
To obtain Mg(OEt)2/FeCl3 mixed supports, Mg(OEt)2
together with different amounts of FeCl3 (see Table 1)
were dispersed in THF, and then, the supports extracted
from the solution by settling and drying under N2 atmo-
sphere.
In order to determine in what extent the ability of a
support to activate a particular catalyst depends on its
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crystal structure, primitive Mg(OEt)2, FeCl3, and one of
the modified support samples, i.e. S-F5, were character-
ized by XRD analysis (see Figure 2). Primitive Mg
(OEt)2 showed sharp peaks centered at 2θ ≈ 11.2, 13.1,
27.5, 29.1, and 30.6 (Figure 2). Three peaks at
2θ ≈ 11.2, 13.1, and 29.1 were associated with the crys-
tal structure of Mg(OEt)2, and two large peaks at
2θ = 27.5 and 30.6° were due to polyethylene film,
which was used to protect the catalyst from exposure to
the atmosphere. After modification of Mg(OEt)2 with
FeCl3 to prepare M-Fe5, all FeCl3 peaks disappeared and
Figure 2. XRD patterns of Mg(OEt)2, FeCl3, and M-Fe5 support samples.
Table 1. Primary composition of prepared supports.
Sample Mg(OEt)2 (wt.%) FeCl3 (wt.%)
S-M 100 0
S-F5 95 5
S-F10 90 10
S-F15 85 15
mixed support showed the same XRD pattern with it in
M; however, it was found that the introduction of FeCl3
caused crystalline structural disorder of Mg(OEt)2,
attributing to the reduction of the intensity of XRD pat-
terns at 2θ ≈ 11.2, 13.1, and 29.1. It can be deduced
from XRD patterns that FeCl3 was dissolved in Mg
(OEt)2 and a new FeCl3/Mg(OEt)2 solid solution was
formed.[31,32] Such a behavior might be ascribed to the
structures in which magnesium was partially replaced by
Fe+2 and not Fe+3, since their ionic radii are very similar
(Mg2+ = 0.88 Å, Fe+2 = 0.84 Å, and Fe+3 = 0.74 Å).
Final catalysts were prepared by reacting support
samples with TiCl4. To this end, two types of catalysts
were prepared: (1) The catalysts were synthesized from
the simple reaction of S-M, S-F5, S-F10, and S-F15
supports with TiCl4, denoted as C-M, C-F5, C-F10, and
C-F15, respectively. (2) Another type of catalysts was
prepared from the reaction of S-F5, S-F10, and S-F15 sup-
port samples with TiCl4 in the presence of secondary
Lewis acid, SiCl4, and named as C-F5-Si, C-F10-Si, and
C-F15-Si, respectively. Surface area of the catalyst
 Designed Monomers and Polymers 5

samples was obtained by BET method and listed in
Table 2. Results showed a significant decrease in the sur-
face area of the catalysts by the addition of FeCl3, in
which surface area was decreased from 467.04 m2/g for
C-M to 380.24, 312.28, 270.18, 415.62, 280.07, and
228.14 m2/g for C-F5, C-F10, C-F15, C-F5-Si, C-F10-Si,
and C-F15-Si, respectively.
Images of the catalyst morphologies generating from
SEM for the synthesized catalysts were shown in
Figure 3(a)–(g). It could be observed that all the
catalysts, doped and undoped with Lewis acids, showed
almost spherical morphology which resemble a normal
catalyst material with mean diameter of about 60 μm.
The surface composition of the obtained catalysts
was obtained by EDX analysis and listed in Table 2. It
was suggested before that, during treatment with SiCl4
and TiCl4, Mg(OEt)2 is mainly converted to MgCl2.[33]
So, besides Ti, Si, and Fe amounts, we decided to calcu-
late Cl content in the catalyst surfaces, as well. Accord-
ing to the information in Table 2, catalysts containing

Table 2. Analysis of the prepared catalysts.

Elemental analysis (wt.%)a

Sample Support structure Surface area (m2/g) Cl Mg Fe Si Ti (wt.%)
C-M S-M 467.04 56.4 10.3 0 0 7.78
C-F5 S-F5 380.24 63.3 9.7 0.8 0 6.40
C-F10 S-F10 312.38 63.4 9.2 1.2 0 4.69
Downloaded by [FU Berlin] at 00:49 08 July 2015

C-F15 S-F15 270.18 63.4 9.0 2.0 0 3.81

C-F5-Si S-F5 415.62 65.9 9.2 1.1 0.7 5.98
C-F10-Si S-F10 280.07 66.2 8.6 1.6 1.2 4.41
C-F15-Si S-F15 228.14 66.1 7.9 2.3 1.0 3.12
a
Obtained from EDX analysis.

Figure 3. SEM images of catalysts (a) C-M, (b) C-F5, (c) C-F10, (d) C-F15, (e) C-F5-Si, (f) C-F10-Si, and (g) C-F15-Si.
 6 R. Bazvand et al.

FeCl3–SiCl4 mixture showed the highest amount of sur-

M-F -S
10
face Cl atom.
It was also observed that the amount of Si in C-F10- 400
Si was higher than that of it in C-F5-Si and C-F15-Si,

Activity (Kg PE / g Ti.h)

even though their amounts were added equally in the
M-F5- S
catalyst preparation step. Furthermore, there was a differ-
ence in the Fe content between primitive amount, which
M-F5
was used in support preparation step, and the amount in
M-F10
the catalyst systems. Fe decrease observed was probably 200 M M M

due to the presence in the support as iron alkyl deriva-

tives which were removed in the course of the catalyst
synthesis.[31] To see the distribution of Fe on the cata-
M-F15-S
lyst surfaces, EDX mapping of catalysts was considered. M-F15

In all catalyst maps, a nearly homogeneous distribution 0

of Fe on catalyst surface was observed. The EDX map- Catalyst
ping of M-Fe5-Si was shown in Figure 4 as a representa-
tive picture.
Figure 5. Activity of synthesized catalysts in slurry phase
UV–visible technique was used to achieve titanium ethylene polymerization.
content of the catalysts (Table 2). Results showed a
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decrease in the Ti content of the samples by applying

FeCl3 modifier. Indeed, lowest Ti content was obtained
for the catalyst containing a mixture of SiCl4 and highest
amount of FeCl3, i.e. C-F15-Si. It is interesting to note
that the addition of SiCl4–FeCl3 mixture might reduce
free-vacancies of Mg(OEt)2 crystallization and lead to
less Ti insertion, which was in agreement with the results
of Phiwkliang et al. [34].
3.2. Ethylene polymerization results
The performance of the catalysts was evaluated in slurry
phase polymerization of ethylene using TEA as cocata-
lyst. Activity results were demonstrated in Figure 5 and
Table 3. As can be seen, the doped catalysts showed an
increase in the activity on increasing FeCl3 content up to
0.8 and 1.6 wt.% (expressed as ferrous wt.%) in M-Fe
and M-Fe–Si type catalysts, respectively. By going to
higher doping concentrations, a drastic drop in the activ-
ity was observed. This finding was in line with other
researchers results which were published before.[35–37]
Furthermore, it was observed that the activity
increase in the presence of FeCl3–SiCl4 mixture was
higher than it in the presence of FeCl3 alone. It is possi-
ble that besides halogen-donating ability of SiCl4 which
acts as promoter in ethylene polymerization, the syner-
gistic effect of double metal halide and metalloid com-
pounds generated more active sites, which were suitable
for ethylene polymerization.

Table 3. The activity of different catalysts in ethylene poly-

merizationa.

Sample Activity (kg Poly/g Ti.h) Increase in activity (%)b

C-M 190 –
C-F5 228 20
C-F10 195 3
C-F15 35 −82
C-F5-Si 300 58
C-F10-Si 450 137
C-F15-Si 41 −78
a
Ethylene polymerization conditions: Wt. of cat: 5 mg, Al/Ti = 180,
n-hexane: 500 mL, ethylene pressure: 5 bar, T = 83 °C.
Figure 4. EDX mapping of M-Fe5-Si. Fe atoms were shown b
(Activity of each catalyst − Activity of catalyst M)/Activity of catalyst
in red and Mg in green colors. M × 100.
 Designed Monomers and Polymers 7

Table 4. Characterization of polyethylenes produced via different catalyst systems.

Sample Mw Mn Mw/Mn Xc (%) Tm (°C) Bulk density (g/mL) Wax amount (%)
C-M 377,000 48,900 7.7 66.9 141.2 0.24 0.88
C-F5 501,000 58,700 8.5 62.9 139.8 0.30 0.58
C-F10 488,000 56,100 8.7 65.4 141.2 0.33 0.33
C-F15 455,000 51,200 8.9 66.1 142.0 0.27 0.49
C-F5-Si 475,000 57,800 8.2 62.4 141.0 0.30 0.33
C-F10-Si 452,000 48,200 9.4 69.1 140.0 0.31 0.34
C-F15-Si 448,000 50,100 8.9 63.0 140.0 0.30 0.26

After successive polymerization tests, the obtained
polyethylenes were characterized by DSC analysis. DSC
curves for all polyethylene samples showed a single peak
indicating no appreciable molecular reorganization dur-
ing heat treatment. Figure 6 shows the representative
DSC diagram of samples prepared with C-M and C-F10-
Si catalysts. Also, Table 4 shows the influence of various
catalytic systems on the Tm and crystallinity (Xc) of the
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3.3. Ethylene/1-hexene copolymerization results
In the next section of this study, we selected C-F10-Si
and C-M as the most active and reference procatalysts,
respectively, and tested even in ethylene/1-hexene
copolymerization experiments in order to assess their
ability in the higher α-olefin insertion. The copolymeriza-
tion results were reported in Table 5. In line with the
homopolymerization results, in the ethylene/1-hexene

obtained polymers. Results indicated that Tm values of
all polyethylenes synthesized from doped catalysts were
similar to it in the unmodified catalyst while that Xc
changed slightly from 66.9% in the unmodified catalyst
to a range of 62.4–69.1% in doped catalysts.
In addition, the Mn and Mw average molecular
weights of the synthesized polyethylenes were measured
by the GPC method. The produced analytical results
were listed in Table 4. The presence of the Lewis acid in
catalyst showed a trend to give a slight increase in the
molecular weight of polyethylenes. This was similar to
the results of Pinyocheep et al. [38] and Phiwkliang
et al. [34], who found that the molecular weight of PE
increases by increasing the amounts of Ti(III) species.
Finally, bulk density of the polymers was measured
by a standard 8.1-mL cylindrical vessel and shown in
Table 4. Results revealed that by adding FeCl3 in the
support structure, bulk density of the polymers increased,
significantly.
copolymerization, the doped catalyst showed much
higher activity of 577 vs. 185 kg Poly/g Ti∙h in reference
catalyst, probably due to the same reasons introduced in
the ethylene homopolymerization section.
Furthermore, it was found that, when M-F10-Si is
used as catalyst, the activity of ethylene/1-hexene
copolymerization increased to 577 kg copoly/g Ti∙h com-
pared with that of ethylene homopolymerization, i.e.
450 kg poly/g Ti∙h. The ‘‘comonomer effect’’ is a curi-
ous phenomenon in which the rate of ethylene polymer-
ization is significantly enhanced by the addition of a
small amount of α-olefin comonomer, while decreases as
the comonomer content in monomer feed increases from
an optimum amount.[39,40]
On the other hand, the presence of comonomer low-
ered the activity of catalyst C-M slightly, from 190 to
185 kg Poly/g Ti∙h, suggesting that the insertion of ethy-
lene was interrupted in this catalyst due to high mole
percent of 1-hexene in monomer feed.[39,41]
The copolymers obtained were characterized and the
results listed in Table 6, which collects melting point,
percentage of crystalline polymer Xc, and comonomer
content. The results showed that the copolymer synthe-
sized with C-M under the same condition, contains a
lower amount of 1-hexene than that with doped catalyst.
This result confirms that the ability of the catalyst to
incorporate bulky comonomer can be improved by dop-
ing of MgCl2(ethoxide type) support with FeCl3 due to

Table 5. Performance of C-M and C-F10-Si catalysts in ethy-

lene/1-hexene copolymerization.

Sample Activity (kg Poly/g Ti∙h) Increase in activity (%)

C-M 185 –
Figure 6. DSC diagram of polymers from catalysts C-M and C-F10-Si 577 211
C-F10-Si.
 8 R. Bazvand et al.

Table 6. Characterization of ethylene\1-hexene copolymers produced via different catalyst systems.

Sample Xc (%) Tm1 (°C) Tm2 (°C) Tc (°C) Comonomer content (%)
C-M 53 138.2 131.6 115.5 2.81
C-F10-Si 44 134.0 128.7 112.8 5.35

higher Lewis acidity of FeCl3. This reduces electron den-
sity on the active center, which is beneficial to the
coordination of more electron-donating-olefin on active
center and lead to higher incorporation efficiency.[42]
The DSC analysis was considered at both the first
and second heating of the copolymer samples which
denoted as 1 and 2 subscripts in the Tm and Xc results,
respectively. As can be seen in Table 6, Tm and Xc were
strongly affected by 1-hexene concentration in the
copolymer chain so that Tm and Xc of the copolymer
produced by C-M catalysts were much higher than them
by C-F10-Si catalyst.
Downloaded by [FU Berlin] at 00:49 08 July 2015
was observed that during interaction with TiCl4 and
SiCl4, it is converted to MgCl2 due to Cl-donating ability
of these compounds.[15,43] To study the Ti–Mg and Ti–
Fe interactions, we considered three model systems:
Mg3–Ti4, Mg2Fe–Ti4, and Fe3–Ti4, see Figure 1 for
labels. These systems mainly differ for the numbers of
Fe atoms involved in FeCl3/MgCl2 mixed supports.
These models were selected according to our XRD and
EDX data, and the data in Refs. [31] and [32] which
suggested that in MCln (M is metal) doped catalysts, a
MCln/MgCl2 solution is formed. DFT studies predicted a
clear binding for all systems, with an EBind of −15.1,

−9.5, and −4.6 kcal mol−1 for systems Mg3–Ti4,

3.4. DFT simulation
In the last part of our manuscript, in order to fulfill the
lack of a clear characterization data, we employed DFT
simulations to assess main interaction occurring in
MgCl2- and MgCl2/FeCl3-supported ZN catalytic sys-
tems. We chose MgCl2, instead of Mg(OEt)2, since it
Mg2Fe–Ti4, and Fe3–Ti4, respectively.
In the next section, to compare better the ability of
MgCl2/TiCl4 and MgCl2/FeCl2/TiCl4 catalytic systems in
ethylene insertion, DFT studies were employed. In order
to model ethylene polymerization using different Fe-
doped ZN catalysts, three different small-sized model
active centers, i.e. Mg3–Ti3–C2H5, Mg2Fe–Ti3–C2H5,

5 0.4
-2.3
+ CH2CH2 -3.1
TS
0

-5
Energy (kcal/mol)

-10
-7.4
-9.1
-15 -10.8

-20
COO
-27.1
-27.4
-25 Fe3-Ti3 -27.3
Mg2Fe-Ti3
Mg3-Ti3
-30 PR

Figure 7. Relative energy profiles for ethylene polymerization using Mg3–Ti3–C2H5, Mg2Fe–Ti3–C2H5, and Fe3–Ti3–C2H5 model
catalysts with BP86/SVP level of calculation.
 Designed Monomers and Polymers 9
Downloaded by [FU Berlin] at 00:49 08 July 2015

Figure 8. Medium-sized model catalysts used in molecular simulation, (a) Mg9–Ti3–CH3, (b) Mg8Fe–Ti3–CH3, and (c) Mg8Fe–
Ti3–CH3-2.

Table 7. TS energy barriers for the insertion of ethylene into with the Ti active center was barrier less and led to 10.8,
different model catalysts with BP86/SVP and PBEh1PBE/ 9.1, and 7.4 kcal mol−1 energy gains, for catalysts Mg3–
TZVP level of calculation. Ti3–C2H5, Mg2Fe–Ti3–C2H5, and Fe3–Ti3–C2H5,
BP86/SVP PBEh1PBE/TZVP respectively. Then, it passed through a four-member ring
structure, which turned out to be the TS. A barrier of
Mg9–Ti3–CH3 6.8 6.1 7.7, 6.8, and 7.8 kcal mol−1 had to be overcome in order
Mg8Fe–Ti3–CH3-1 5.8 5.1
Mg8Fe–Ti3–CH3-2 6.8 6.1 to insert the entering monomer into the Ti–C bond in the
catalysts Mg3–Ti3–C2H5, Mg2Fe–Ti3–C2H5, and Fe3–
Ti3–C2H5, respectively. The final products were charac-
terized and found to be nearly isoenergetic in all cases.
and Fe3–Ti3–C2H5 were utilized. Energy diagrams for These results indicated that by partially doping of MgCl2
ethylene insertion using different model catalysts were with Fe, although the coordination energy was increased,
shown in Figure 7. The complexation of the monomer insertion of ethylene required rather smaller activation
 10 R. Bazvand et al.

(nearly 1 kcal mol−1). Further, models have been pro-

posed that explain in a simple way the monomer inser-
tion promotion by Fe doping agent, when located in the
near proximity of a TiCl4 molecule adsorbed on the
MgCl2 surface.
To test whether the energy barrier of the TSs could
depend on the chosen GGA BP86 functional, we local-
ized the TSs with the HGGA PBEh1PBE functional,
since we found earlier that it gives the best performance
in reproducing the main interactions occurring in ZN cat-
alytic systems.[1] The results were tabulated in Table 7.
Also, in this case, ETS of ethylene insertion in Mg8Fe–
Ti3–CH3 model was 1.0 kcal mol−1 lower in energy than
that in Mg9–Ti3–CH3 model. Then, the numbers we
calculated indicate that the difference between the TSs
energies in undoped and doped catalysts is somewhat
independent from the computational approach used.
We also studied the effect of Fe doping on the electron
density of Ti active center, in different model catalysts of
Downloaded by [FU Berlin] at 00:49 08 July 2015

Figure 1. The Mulliken charges on Ti in the active cata-

lysts on moving from Mg3–Ti3–C2H5 to the Mg2Fe–Ti3–
C2H5 and Fe3–Ti3–C2H5 active centers increased from
−0.349 to −0.189 and −0.035, respectively. This increase
in the Mulliken charge could be responsible for the activ-
ity increase in partially doped catalyst, while that in highly
doped catalyst, it seems that other factors rather that
energy, 6.8 vs. 7.7 kcal mol−1. Concluding this section,
charge density on Ti may play main role.
calculations suggest that different catalysts have rather
As the final step, we tried to explore possible role of
similar insertion barriers (within 1 kcal mol−1). This indi-
SiCl4 in activity increase of ZN catalyst. The model cata-
cates that the doping does not alter significantly the
lyst that we selected for the coordination of SiCl4 into
capability of the Ti to insert ethylene monomer.
active catalyst was shown in Figure 9. By attaching
After having explored the effect of doping amount
SiCl4 molecule to our model catalyst, the Mulliken
on the energy profile of ethylene insertion, we have tried
charge on Ti decreased from −0.189 in uncoordinated
to study the effect of MgCl2 cluster size on the monomer
system to the −0.206 in SiCl4 coordinated system. We
insertion barrier. Furthermore, besides cluster size, effect
can conclude from these data that SiCl4 role in activity
of possible doping positions on the TS energy of ethy-
increase of the modified catalysts is not related to its
lene insertion was studied, as well. Here, for the sake of
Lewis acidic property, but can be due to its Cl-donating
brevity, we focused only on the TS energies, while
ability since the homolytic dissociation energy of C–Cl
coordination and insertion steps were not considered. For
bond in chlorocyclohexane, which has been known as
these calculations, we abandoned small (MgCl2)3 model
the most efficient activator,[15] is only 8.2 kcal mol−1
and used a more realistic model containing a cluster with
lower than homolytic dissociation of Si–Cl bond in SiCl4
9 MgCl2 units. Our studied models were shown in
(84.5 vs. 92.7 kcal mol−1). So from this section, we can
Figure 8(a)–(c). Figure 8(a) is a representative model of
conclude that SiCl4 role in the activation of ZN catalysts
undoped catalyst, while Figure 8(b) and (c) differ in the
can be due to its oxidizing ability in reactivating Ti(II)
location of Fe atom, relative to the Ti active center,
center by oxidizing it into Ti(III) and Ti(IV), reintroduc-
among MgCl2 surface. Calculation results with BP86/
ing it into the active cycle. Reactivation of Ti(II) centers
SVP level of theory showed that a barrier of 6.8, 5.8,
by Cl-containing molecules was fully studied in our
and 6.8 kcal mol−1 have to be overcome in order to
previous article [24] and is not more considered here.
insert ethylene monomer into Ti–C bond in the Mg9–
Ti3–CH3, Mg8Fe–Ti3–CH3, and Mg8Fe–Ti3–CH3-2
model catalysts, respectively. From these data, one can 4. Conclusion
conclude that, although changing cluster size affected TS
In this study, first novel carrier materials were synthe-
absolute values (from 7.7 to 6.8 and from 6.8 to
sized by doping Mg(OEt)2 with different amounts of
5.8 kcal mol−1), ΔETS, i.e. TS energy difference between
FeCl3. Then, final catalysts were prepared by reacting
undoped and doped catalysts, remained unchanged
support samples with TiCl4. In this way, two types of
 Designed Monomers and Polymers
catalysts were prepared: (1) Catalysts synthesized from
the simple reaction of the supports with TiCl4 were
denoted as C-M, C-F5, C-F10, and C-F15. (2) Another
type of catalysts was prepared from the reaction of the
support samples with TiCl4 in the presence of secondary
Lewis acid, SiCl4, and named as C-F5-Si, C-F10-Si, and
C-F15-Si, respectively. Then, their efficiency was investi-
gated toward catalytic activity in ethylene polymerization
as well as some properties of the polymers obtained
thereof. Catalytic activity in ethylene polymerization was
in the sequence of C-F10-Si > C-F5-Si > C-F5 > C-
F10 > C-M > C-F15 > C-F15-Si. Furthermore, character-
ization of the polymers showed that catalyst modification
increases the bulk density and molecular weights,
reduces wax amount, but does not affect on the melting
temperature of resulting polymers.
In the next step, ethylene/1-hexene copolymerization
was carried out using C-M and C-F10-Si as reference
and most efficient procatalysts, respectively. Results
Downloaded by [FU Berlin] at 00:49 08 July 2015
showed higher activity as well as higher 1-hexene
incorporation for modified catalyst in comparison with
unmodified one.
In some cases, to shed light on possible interaction
of TiCl4 with doped and undoped catalysts, as well as
their efficiency in ethylene polymerization, molecular
simulation was performed using DFT method. It is the
first time that DFT simulation was used to unravel basic
interactions in these kinds of catalysts.
Acknowledgments
The authors thank MOLNAC (www.molnac.unisa.it) for its
computer facilities and also Jam petrochemical company for
comonomer content analysis.
Disclosure statement
No potential conflict of interest was reported by the authors.
Funding
This work was supported by Iran National Science Foundation
(INSF) [grant number 92031703].
Supplemental data
Supplemental data for this article can be accessed here http://
dx.doi.org/10.1080/15685551.2015.1041089.
References
[1] Correa A, Bahri-Laleh N, Cavallo L. How well can DFT
reproduce key interactions in Ziegler–Natta systems?
Macromol. Chem. Phys. 2013;214:1980–1989.
[2] Arzoumanidis G. Amoco CD commercial polypropylene
catalyst tailor-made for the Amoco-Chisso gas phase pro-
cess. Polyolefins J. 2014;1:131–137.
11
[3] Woo JH, Hong SC. Study on immobilized metallocene and
single-site catalysts for the preparation of ultra-high molecu-
lar weight polyethylene at various polymerization condi-
tions. Polym.-Plast. Technol. Eng. 2011;50:1557–1563.
[4] Xiao A, Zhou S, Zheng Q, Shen Y, Zhang W. Recent
research progress of branched and functional branched
polyethylene prepared using Ni- and Pd-based catalysts.
Polym.-Plast. Technol. Eng. 2010;49:1540–1551.
[5] Rahbar A, Nekoomanesh-Haghighi M, Bahri-Laleh N,
Abedini H. Effect of water on the supported Ziegler–Natta
catalysts: optimization of the operating conditions by
response surface methodology. Catal. Lett. 2015;145:
1186–1195.
[6] Shafiee M, Ramazani SAA. Optimization of UHMWPE/-
graphene nanocomposite processing using Ziegler–Natta
catalytic system via response surface methodology.
Polym.-Plast. Technol. Eng. 2014;53:969–974.
[7] Sharma A, Singh S, Singh G, Gupta VK. Polypropylene
resin flowability improvement through catalyst morphol-
ogy. Polym.-Plast. Technol. Eng. 2011;50:418–422.
[8] Tanase S, Katayama K, Inasawa S, Okada F, Yamaguchi
Y, Sadashima T, Yabunouchi N, Konakazawa T, Junke T,
Ishihara N. New synthesis method using magnesium
alkoxides as carrier materials for Ziegler–Natta Catalysts
with spherical morphology. Macromol. React. Eng.
2008;2:233–239.
[9] Németh Sn, Feil B, Árva P, Abonyi J. Effects of catalyst
activity profiles on the operating conditions of an indus-
trial polymerization reactor. Polym.-Plast. Technol. Eng.
2006;45:1301–1306.
[10] Hadian N, Hakim S, Nekoomanesh-Haghighi M, Bahri-
Laleh N. Storage time effect on dynamic structure of
MgCl2.nEtOH adducts in heterogeneous Ziegler–Natta
catalysts. Polyolefins J. 2014;1:33–41.
[11] Ma Z, Wang L, Wang W, Wang J, Yu H. Study of propy-
lene polymerization catalyzed by spherical MgCl2-sup-
ported Ziegler–Natta catalyst system: preparation of
spherical support. Polym.-Plast. Technol. Eng. 2005;44:
1475–1483.
[12] Wang J, Wang L, Feng L, Gu X, Yu H. Studies on syn-
thesis of low isotactic polypropylene by using a novel
MgCl2-supported and low Ti-loading catalyst. Polym.-
Plast. Technol. Eng. 2005;44:501–510.
[13] Yu H, Wang L, Ye Z, Ma Z, Jiang S, Wang J, Feng L, Gu
X. Study on morphology and particle size distribution of
polypropene catalyzed by novel spherical Ziegler–Natta
catalyst. Polym.-Plast. Technol. Eng. 2004;43:1115–1128.
[14] Zhao Z, Wang L, Wang J, Gao H, Yu H, Chen T, Dong
X. Study on the microstructures of polypropylene synthe-
sized by a novel MgCl2-supported and low Ti-loading
Ziegler–Natta catalyst. Des. Monomers Polym. 2007;10:
477–486.
[15] Bahri-Laleh N, Arabi H, Mehdipor-Ataei S, Nekooma-
nesh-Haghighi M, Zohuri G, Seifali M, Akbari Z. Activa-
tion of Ziegler–Natta catalysts by organohalide promoters:
a combined experimental and density functional theory
study. J. Appl. Polym. Sci. 2012;123:2526–2533.
[16] Patil HR, Vyas PB, Bhajiwala HM, Gupta V. Alkoxy
silanes as external donors for polypropylene procatalyst:
study on polymerization performance and effect on resin
properties. Polym.-Plast. Technol. Eng. 2012;51:466–472.
[17] Parada A, Rajmankina T, Chirinos J, Morillo A, Fernán-
dez JG. Catalytic systems based on TiCl4/MgCl2/SiCl4-
n(OR)n for olefin polymerization. Des. Monomers Polym.
2003;6:1–10.
 12 R. Bazvand et al.
[18] Sun T, Wang L, Dong X, Wang W. An insight into the
chain-propagation mechanism of propylene polymerization
catalyzed by traditional Ti-based Ziegler–Natta catalysts in
view of recently developed catalysts. Des. Monomers
Polym. 2006;9:117–127.
[19] Xiao A, Wang L, Liu Q, Yu H, Dong X. Synthesis of low
isotactic polypropylene using MgCl2/AlCl3-supported
Ziegler–Natta catalysts prepared using the one-pot milling
method. Des. Monomers Polym. 2008;11:139–145.
[20] Garoff T, Leinonen T. Mn doping of the Ziegler–Natta PP
catalyst support material. J. Mol. Catal. A: Chem.
1996;104:205–212.
[21] Shamiri A, Chakrabarti M, Jahan S, Hussain M,
Kaminsky W, Aravind P, Yehye W. The influence of Zieg-
ler–Natta and metallocene catalysts on polyolefin struc-
ture, properties, and processing ability. Materials.
2014;7:5069–5108.
[22] Bahri-Laleh N, Seifali Abbas-Abadi M, Nekoomanesh
-Haghighi M, Akbari Z, Tavasoli MR, Mirjahanmardi SH.
Effect of halocarbon promoters on polyethylene properties
using MgCl2 (ethoxide type)/TiCl4/AlEt3/H2 catalyst sys-
tem. J. Appl. Polym. Sci. 2010;117:1780–1786.
[23] ASTM D 2238 –921999. Standard test methods for absor-
Downloaded by [FU Berlin] at 00:49 08 July 2015
bance of polyethylene due to methyl groups at 1378
cm−1. ASTM International: West Conshohocken, PA;
2012.
[24] Bahri-Laleh N, Correa A, Mehdipour-Ataei S, Arabi H,
Nekoomanesh-Haghighi M, Zohuri GH, Cavallo L.
Moving up and down the titanium oxidation state in Zie-
gler−Natta catalysis. Macromolecules. 2011;44:778–783.
[25] Bahri-Laleh N, Nekoomanesh-Haghighi M, Mirmoham-
madi SA. A DFT study on the effect of hydrogen in ethy-
lene and propylene polymerization using a Ti-based
heterogeneous Ziegler–Natta catalyst. J. Organomet.
Chem. 2012;719:74–79.
[26] Frisch MJ, Trucks GW, Schlegel HB. Gaussian 09. Pitts-
burgh (PA); 2009.
[27] Perdew JP. Density-functional approximation for the
correlation energy of the inhomogeneous electron gas.
Phys. Rev. B. 1986;33:8822–8824.
[28] Schäfer A, Horn H, Ahlrichs R. Fully optimized con-
tracted Gaussian basis sets for atoms Li to Kr. J. Chem.
Phys. 1992;97:2571.
[29] Küchle W, Dolg M, Stoll H, Preuss H. ECP SDD. J.
Chem. Phys. 1994;100:7535.
[30] Ernzerhof M, Perdew JP. Generalized gradient approxima-
tion to the angle- and system-averaged exchange hole. J.
Chem. Phys. 1998;109:3313–3320.
[31] Fregonese D, Bresadola S. Catalytic systems supported on
MgCl2 doped with ZnCl2 for olefin polymerization. J.
Mol. Catal. A: Chem. 1999;145 265–271.
[32] Chen Y-P, Fan Z-Q, Liao J-H, Liao S-Q. Molecular
weight distribution of polyethylene catalyzed by Ziegler–
Natta catalyst supported on MgCl2 doped with AlCl3. J.
Appl. Polym. Sci. 2006;102:1768–1772.
[33] Zohuri GH, Ahmadjo S, Jamjah R, Nekoomanosh M.
Structural study of mono- and bi-supported Ziegler–Natta
catalysts of MgC12/SiO2/TiC14/donor systems. Iran
Polym. J. 2001;10:149–155.
[34] Phiwkliang W, Jongsomjit B, Praserthdam P. Effect of
ZnCl2- and SiCl4-doped TiCl4/MgCl2/THF catalysts for
ethylene polymerization. J. Appl. Polym. Sci.
2013;130:1588–1594.
[35] Phiwkliang W, Jongsomjit B, Praserthdam P. Synergistic
effects of the ZnCl2–SiCl4 modified TiCl4/MgCl2/THF cat-
alytic system on ethylene/1-hexene and ethylene/1-octene
copolymerizations. Chin. J. Polym. Sci. 2014;32:84–91.
[36] Ribour D, Monteil V, Spitz R. Strong activation of
MgCl2-supported Ziegler–Natta catalysts by treatments
with BCl3: evidence and application of the “cluster”
model of active sites. J. Polym. Sci., Part A: Polym.
Chem. 2009;47:5784–5791.
[37] Chen Y-P, Fan Z-Q. Ethylene/1-hexene copolymerization
with TiCl4/MgCl2/AlCl3 catalyst in the presence of hydro-
gen. Eur. Polym. J. 2006;42:2441–2449.
[38] Pinyocheep J, Ayudhya SKN, Jongsomjit B, Praserthdam
P. Observation on inhibition of Ti3+ reduction by fumed
silica addition in Ziegler–Natta catalyst with in situ ESR.
J. Ind. Eng. Chem. 2012;18:1888–1892.
[39] Cho HS, Lee WY. Synthesis of inorganic MgCl2–alcohol
adduct via recrystallization method and its application in
supported organometallic catalysts for the polymerization
of ethylene with 1-hexene. J. Mol. Catal. A: Chem.
2003;191:155–165.
[40] Palza H, Velilla T, Quijada Rl. Dynamic model of the
copolymerization of propylene and 1-hexene with the
Me2Si(2-Me-Ind)2ZrCl2 catalytic system: effect of 1-hex-
ene concentration. Polym.-Plast. Technol. Eng. 2006;45:
1233–1241.
[41] Moreno J, van Grieken R, Carrero A, Paredes B. Ethylene
polymerization by metallocene catalysts supported over
siliceous materials with bimodal pore size distribution.
Macromol. Symp. 2011;302:198–207.
[42] Senso N, Praserthdam P, Jongsomjit B, Taniike T, Terano
M. Effects of Ti oxidation state on ethylene, 1-hexene
comonomer polymerization by MgCl2-supported Ziegler–
Natta catalysts. Polym. Bull. 2011;67:1979–1989.
[43] Ghasemi Hamedani N, Behroozi Fard Moghaddam M,
Marandi R, Azimfar F, Abedi S, inventors. Ziegler catalyst
and method of synthesizing the same patent 2013/
0030134 A1. 2013.