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Catalytic systems based on

TiCl4/MgCl2/SiCl4-n(OR)n for
olefin polymerization
A. Parada , T. Rajmankina , J. J. Chirinos , A.
Morillo & J. G. Fernández
Published online: 02 Apr 2012.

To cite this article: A. Parada , T. Rajmankina , J. J. Chirinos , A. Morillo & J. G.

Fernández (2003) Catalytic systems based on TiCl4/MgCl2/SiCl4-n(OR)n for olefin
polymerization , Designed Monomers and Polymers, 6:1, 1-10

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 Designed Monomers and Polymers, Vol. 6, No. 1, pp. 1 – 10 (2003)
Ó VSP 2003.
Also available online - www.vsppub.com

Catalytic systems based on TiCl4 /MgCl2 /SiCl4¡n (OR) n

for oleŽ n polymerization

A. PARADA ¤ , T. RAJMANKINA, J. J. CHIRINOS, A. MORILLO

Downloaded by [University of Regina] at 21:56 18 November 2014

and J. G. FERNÁNDEZ
Laboratorio de Polímeros, Departamento de Química, Facultad de Ciencias, La Universidad
del Zulia, Maracaibo, Venezuela

Abstract—The effect of the alcohol nature in TiCl 4 catalysts supported on MgCl2 , modiŽ ed by the
recrystallizationtechnique with SiCl 4 , has been investigated in terms of activity and tacticity control.
A series of alcoholic solutions of MgCl2 , using 1-hexanol, t-butanol, butanol, iso-propanol, propanol
and ethanol, were recrystallized with SiCl 4 and the supports were subsequently impregnated with
TiCl 4 . Also, as a way of comparison, catalysts were prepared from solutions of MgCl2 in 1-hexanol
recrystallizedby solvent evaporation and quick cooling. The supports and catalysts were characterized
by infrared and energy dispersive scanning (EDS). Polymerization of ethylene and propylene was
performed under different temperature and pressure conditions, using triethylaluminium as a co-
catalyst in the absence of electron donors. The catalytic activity depended strongly on the length of
the alkyl group and the nature of the isomeric alcohol used in the treatment of the support. The yield
and isotacticity of the polypropylene are governed by polymerization parameters such as pressure and
support treatment. The EDS results conŽ rmed the presence of alkoxysilanes in the catalysts treated
with SiCl 4 .

Keywords: OleŽ n polymerization; Ziegler–Natta catalyst; recrystallization techniques; catalytic

support; alkoxysilanes.

1. INTRODUCTION

Among the various preparation methods of highly active MgCl2 supports, the
recrystallization method is the most recent [1 – 11]. The method consists in chemical
activation through the reaction of crystalline MgCl2 with proton electron donor
alcohol-type compounds until dissolution, followed by controlled regeneration of
the active support through recrystallization by solvent evaporation [1 – 5] or quick
cooling [5 – 11], andd Ž nally TiCl4 impregnation. Although the recrystallization

¤
To whom correspondence should be addressed. Fax: (58-261) 798-5908; e-mail: aparada@luz.ve
 2 A. Parada et al.

method has strong merit in yielding polymers with good morphology, alcohol
elimination by these techniques is not complete and its presence in the support
is undesirable, as it reacts with TiCl4 during impregnation, producing titanium
alkoxides, inactive for polymerization [12]. Our research team has recently studied
the preparation of Ziegler– Natta catalysts for the polymerization of oleŽ ns through
TiCl4 impregnation on MgCl2 recrystallized with silicon tetrachloride from alcohol
solutions, attaining complete dealcoholation and a higher polyethylene yield than
traditional recrystallization techniques [5].
In the present study, we investigated the effect of the nature of alcohol in
TiCl4 catalysts supported on MgCl2 , modiŽ ed by the recrystallization with SiCl4
from their solutions in different alcohols, in terms of activity improvement and
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tacticity control. A series of alcoholic solutions of MgCl2 , using 1-hexanol,

t-butanol, butanol, iso-propanol, propanol, and ethanol, were recrystallized with
SiCl4 and the supports were subsequently impregnated with TiCl4 . Also, as a
means of comparison, catalysts were prepared from solutions of MgCl2 in 1-hexanol
recrystallized by solvent evaporation and quick cooling. The catalysts were used in
the polymerization of ethylene and propylene, using triethylaluminium (TEA) as a
co-catalyst in the absence of electron donors.

2. EXPERIMENTAL

2.1. Materials
Anhydrous MgCl2 , TiCl4 , SiCl4 (Aldrich), and AlEt3 (Schering) were used without
further puriŽ cation. Heptane, hexane, and iso-octane (Aldrich) were distilled from
Na/benzophenone and stored over molecular sieves (4 Å). 1-Hexanol, t-butanol,
butanol, isopropanol, 1-propanol and ethanol (Riedel – de Haen) were used after
distillation and stored over molecular sieves. Polymerization-grade ethylene and
propylene (Matheson) were used after passing them through columns of molecular
sieves. Standard Schlenk techniques and high-purity nitrogen were used for the
handling of all compounds.
MgCl2 was dried at 150± C under vacuum for 48 h and then dissolved in an
alcohol/iso-octane mixture at re ux temperature under stirring for 4 h. The
alcoholic solutions were recrystallized with a SiCl4 solution in hexane, in a 1 : 1
(v/v) proportion, under stirring until a jelly precipitate was formed. Then the
recrystallized supports were impregnated with TiCl4 in a Ti/Mg = 1 molar relation,
and put under stirring at re ux temperature for 2 h. The impregnated supports
were washed several times with heptane, with periods of stirring and suspended
solid sedimentation to eliminate any excess TiCl4 . Finally, catalyst samples were
suspended in heptane, for use in oleŽ n polymerization.
Other catalysts were prepared through other traditional techniques in order to
compare the SiCl4 recrystallization technique. For that purpose, MgCl2 was
dissolved in 1-hexanol and recrystallized by solvent evaporation and temperature
 Catalytic systems based on TiCl 4 /MgCl2 /SiCl4¡n (OR)n 3

reduction. Afterwards, the catalysts were successively washed with hexane to

eliminate any trace of alcohol; TiCl4 was then added and they were washed again.
Also, for comparison, a catalyst was prepared, denoted by RTi, where the MgCl2
was directly impregnated with TiCl4 without alcohol treatment.

2.2. Polymerization reactions

Ethylene and propylene polymerizations were carried out using 10 ¹mol Ti to an
Al/Ti D 100 molar relation, under different temperature and pressure conditions.
Ethylene polymerization was carried out in a 100 ml glass reactor, with magnetic
agitation, in 50 ml of n-hexane at 25± C and 1 atm of pressure for 30 min. For the
polymerization of propylene, a 1 l stainless steel autoclave (Büchi) was used, which
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was equipped with an external jacket for water recirculation from a thermostatic
Julabo bath to regulate the internal temperature. During polymerization, the
temperature was kept within §0:1o C; other experimental conditions are indicated
in the tables.

2.3. Characterization
The Ti content in the catalysts was determined colorimetrically. A Perkin-Elmer
1725 spectrophotometer was used to measure the IR spectra under a nitrogen
atmosphere. Catalyst samples were prepared as a nujol mull and held between
NaCl plates. The isotactic index (II, wt% of heptane-insoluble polypropylene) was
determined through Soxhlet extraction for 8 h. EDS spectra were recorded by an
EDS Kevex-Delta Class-III Analyzer coupled to a scanning electron microscope
(Hitachi S2500).

3. RESULTS
Table 1 shows the conditions and catalyst experimental results for the ethylene and
propylene polymerization reactions. All catalysts modiŽ ed by the recrystallization
Table 1.
In uence of the alcohol nature on the catalyst properties

Catalyst System Ti Activitya II

(%wt) C2 C3 (%)
RTi MgCl2 /TiCl4 1.8 2.03 0.33 76
RC6Si MgCl2 /1-hexanol/SiCl 4 /TiCl4 10.8 23.06 18.9 79
RC4tSi MgCl2 /t-butanol/SiCl 4 /TiCl4 4.9 2.06 —
RC4Si MgCl2 /butanol/SiCl 4 /TiCl4 3.1 20.88 24.7 82
RC3iSi MgCl2 /iso-propanol/SiCl4 /TiCl4 4.4 18.40 —
RC3Si MgCl2 /propanol/SiCl4 /TiCl4 5.0 16.20 6.4 84
RC2Si MgCl2 /ethanol/SiCl 4 /TiCl4 2.6 11.90 5.3 67
a kg polymer/g Ti¢h¢atm).
 4 A. Parada et al.

4 h=re ux
MgCl2 C n ROH ¡! MgCl2 ¢ XROH (1)
20 ± C
MgCl2 ¢ XROH C SiCl4 ¡! MgCl2 ¢ Si.OR/n Cl4¡n (2)
¡HCl
2 h=re ux
MgCl2 ¢ Si.OR/n Cl4¡n C TiCl4 ¡! MgTi cat (3)

Scheme 1. Equations postulated to describe the reactions between the catalyst components [5].

technique were more active than the reference catalyst (RTi); some reached values
ten times higher. The activities were strongly determined by the nature of the
alcohol used in the support treatment; catalysts obtained through alcohols with
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linear chains showed the highest values as a function of chain length, while those
with branched structures were less active. These factors show contributions of
an electronic type or steric hindrance that in uence the complexation behaviour
of alcohols with MgCl2 and therefore affect the dealcoholation capacity of silicon
tetrachloride and the corresponding alkoxysilane structure; consequently, they can
deactivate or limit monomer approximation and insertion into the active centre of
the growing chain.
Scheme 1 shows the equations postulated to describe the reactions among catalyst
components during the preparation stages [5]. According to Gupta, Shashikant
and Ravindranathan [11], anhydrous MgCl2 reacts with aliphatic alcohols to give
adducts of different stoichiometries (Eq. 1). The stoichiometric changes depend on
the chain length of the alkyl group and on the different alcohol isomer structures.
SiCl4 produces dealcoholation of the MgCl2 ¢XROH adduct, directly generating
alkoxysilanes (Eq. 2) during the catalyst preparation. On the one hand, the
elimination of alcohols avoids their reaction with TiCl4 during impregnation to
produce titanium alkoxides, which are inactive during polymerization [12]. On the
other, alkoxysilanes can act as internal electron donors [13– 15] that orientate the
insertion of ®-oleŽ n. A very important aspect is the isotactic index. According to
the values obtained, the majority of the modiŽ ed catalysts presented values higher
than that of the reference catalyst.
Table 2 shows the results obtained during propylene polymerization under differ-
ent temperature and pressure conditions with catalysts obtained by different recrys-
tallization techniques. The contents of the supported titanium obtained from recrys-
tallization of the MgCl2 solution by cooling (RC6T) showed the lowest value. The
one recrystallized by evaporation (RC6E) showed an intermediate value, and the
one recrystallized by precipitation with SiCl4 (RC6Si) the highest content. This be-
haviour can be related, on the one hand, to the level of crystalline structure disorder
and the size of the MgCl2 crystals and, on the other, to the degree of dealcoholation
of MgCl2 ¢XROH adducts during the process of impregnation [2, 3, 5, 10] for each
support treatment.
To conŽ rm the dealcoholation effect, conditioned by the particular technique of
recrystallization, a comparative study was carried out by infrared spectroscopy of
 Catalytic systems based on TiCl 4 /MgCl2 /SiCl4¡n (OR)n 5

Table 2.
Propylene polymerization with catalysts obtained by different recrystallizationtechniques

Catalyst Ti Tp Pp Activity II
(%wt) (± C) (atm) (%)
25 1 4.3 65
RC6T 7.0 70 2 6.2 74
70 40 19.1 91
25 1 4.7 68
RC6E 9.8 70 2 5.8 64
70 40 15.3 92
25 1 8.4 70
RC6Si 11.3 70 2 10.1 79
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70 40 34.1 96

the different samples of catalysts. As these catalysts are very sensitive to humidity,
it was necessary to work under a high-purity nitrogen atmosphere to maintain
anaerobic conditions. The IR spectra of the RC6E and RC6T catalysts were very
similar. They showed a band around 3500 cm¡1 corresponding to the hydroxyl
group of alcohol and a strong band at 1065 cm¡1 , typical of a C–O single bond
stretching mode corresponding to the titanium alkoxide [5, 16]. In the IR spectrum
of RC6Si, the band of the hydroxyl group disappeared and at the same time a
band centred on 1090 cm¡1 , of the C–O bond, was observed corresponding to the
formation of alkoxysilanes.
The recrystallization techniques signiŽ cantly affected the activity of the catalysts,
the most active ones being those recrystallized by SiCl4 precipitation, followed
by those recrystallized by cooling and, lastly, those by solvent evaporation. The
combined effect of temperature and pressure clearly favoured, as expected, the
catalytic activities, maintaining the behaviour pattern determined by the kind of
catalyst.
For the catalysts in this study, according to the contents of supported titanium,
chemical factors such as the formation of inert complexes, e.g. titanium alkoxides,
which do not participate in the formation of active sites, were decisive in a
good catalytic performance. Thus, the RC6T and RC6E catalysts, which after
washing still contained some alcohol traces as an integral part of the support
in adduct form, MgCl2 ¢XROH, reacted during the impregnation with TiCl4 to
give the corresponding titanium alkoxide, Cl3 Ti–O–(1-hexyl), inactive for the
polymerization and the lower presence of free TiCl4 . According to Garoff et al. [12],
Cl3 Ti–OR not only increases the catalyst weight, but also blocks the remaining
active centres in the activated support material. However, in the preparation of the
RC6Si catalyst, SiCl4 reacted vigorously with the alcohol from the adduct, with the
liberation of HCl, to form SiCl4¡n (O-1-hexyl)n . It is important to mention that, in
this case, the system precipitated very slowly as an expanded gel and kept a sponge
shape after several washes. It is expected that under such conditions MgCl2 crystals
 6 A. Parada et al.

are more exposed to TiCl4 during the impregnation process, generating a higher
number of active centres, a result that is re ected in greater activity in this catalyst.
Young and Ray [17] conŽ rmed that the catalyst nature, monomer concentration,
and polymerization temperature, among others, in uenced the catalytic activity as
well as stereospeciŽ city. In our study, we observed that the isotacticity, in particular,
depended mainly on the propylene pressure. The values obtained in bulk-phase
polymerization are very close to those reported in the literature for the processes of
industrial propylene polymerization.
The fact that the greatest isotacticity values were obtained with the RC6Si catalyst
leads us to suspect that it is due to the presence of alkoxysilanes. Therefore,
our results could be explained via research done by Seppala and co-workers [15]
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on the effects of various alkoxysilane compounds on the active sites of a highly

isospeciŽ c Ziegler –Natta catalyst. Their research suggests that the alkoxysilanes
formed will complex into the MgCl2 surface and act as internal bases, blocking off
the vacant sites on the surface of MgCl2 from reaction with TiCl4 , thus preventing
the formation of speciŽ c sites and possibly stabilizing some active isospeciŽ c sites
in the vicinity of the donor.

3.1. EDS analysis

To conŽ rm the presence of silicon compounds in catalysts treated with SiCl4 ,

EDS studies were carried out on the recrystallized support samples before and
after impregnation. In some cases, the recrystallized support was washed before
impregnation, in order to eliminate the alcohol. In this case, we wanted to know the
permanence of the alkoxysilanes after the washes. Figure 1 shows the EDS spectra
of pure MgCl2 (Fig. 1a) and the MgCl2 samples recrystallized with SiCl4 from their
solutions in 1-hexanol, after the Ž rst (Fig. 1b) and Ž fth (Fig. 1c) wash, respectively.
It can be seen that the alkoxysilanes still remain in the support after the Ž fth wash.
Fig. 2 shows spectra of the support that was recrystallized, washed, impregnated
with TiCl4 , and then washed once (Fig. 2a) and Ž ve times (Fig. 2b) before the
EDS analysis. The reduction of the Ti and Si peaks is evident, as expected, but
a signiŽ cant quantity of Si remains as part of the catalyst.
Finally, Fig. 3 shows the results for the catalyst obtained by impregnation from the
recrystallized support, without washing. The spectra in Figs 3a and 3b correspond to
the catalyst after the Ž rst and Ž fth wash, respectively, to eliminate the non-supported
TiCl4 . In Fig. 3a, a large peak corresponding to Si is observed in comparison
with the Ti peak, due, of course, to the fact that alkoxysilanes were not extracted
before impregnation. After the Ž fth wash, the Si signal was considerably reduced,
but it was still rather signiŽ cant. These results are clear evidence that some of
the alkoxysilanes formed during the recrystallization stage remain in the catalyst,
possibly complexed to the MgCl2 surface.
 Catalytic systems based on TiCl 4 /MgCl2 /SiCl4¡n (OR)n 7
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Figure 1. EDS spectra of the recrystallized support: (a) pure MgCl2 ; (b) MgCl2 ¢XROH/SiCl 4 after
the Ž rst wash; (c) MgCl2 ¢XROH/SiCl 4 after the Ž fth wash.
 8 A. Parada et al.
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Figure 2. EDS spectra of the recrystallized catalyst: (a) MgCl2 ¢XROH/SiCl 4/TiCl4 , Ž rst wash after
impregnation on the washed– recrystallized support; (b) MgCl2 ¢XROH/SiCl 4 /TiCl4 , Ž fth wash after
impregnation on washed– recrystallized support.
 Catalytic systems based on TiCl 4 /MgCl2 /SiCl4¡n (OR)n 9
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Figure 3. EDS spectra of the recrystallized catalyst: (a) MgCl2 ¢XROH/SiCl 4/TiCl4 , Ž rst wash after
impregnation; (b) MgCl2 ¢XROH/SiCl 4/TiCl4 , Ž fth wash after impregnation.
 10 A. Parada et al.

4. CONCLUSIONS

The catalytic activity for the polymerization of ethylene and propylene depended
strongly on the nature of the alcohol used in the treatment of the support. The iso-
tactic indices for propylene polymerized with the alcohol-modiŽ ed catalysts were
higher than that of the reference catalyst. The catalyst obtained by recrystallization
with SiCl4 was more stereoselective than those obtained by solvent evaporation and
rapid-cooling recrystallization. The II and EDS results support the idea of alkoxysi-
lane formation through the reaction of alcohol and SiCl4 during the preparation of
catalysts.

Acknowledgements
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We thank Consejo Nacional de Investigaciones CientíŽ cas (C0NICIT) and Consejo

de Desarrollo de la Universidad del Zulia (CONDES-LUZ) for Ž nancial support.

REFERENCES
1. H. S. Woo, J. S. Chung, I. K. Song and W. Y. Lee, Macromol. Chem. Phys. 19, 3765 (1995).
2. J. S. Chung, I. K. Song and W. Y. Lee, Macromol. Chem. Phys. 196, 1205 (1995).
3. J. H. Choi, J. S. Chung, H. W. Shin, I. K. Song and W. Y. Lee, Eur. Polym. J. 32, 405 (1996).
4. K. Czaja and B. Krol, Macromol. Chem. Phys. 199, 451 (1998).
5. A. Parada, T. Rajmankina and J. Chirinos, Polym. Bull. 43, 231 (1999).
6. K. S. Kang, M. A. Ok and S. K. Ihm, J. Appl. Polym. Sci. 40, 1330 (1990).
7. D. N. Taviera Magalhaes, O. Do Coutto Filho and F. M. B. Coutinho, Eur. Polym. J. 27, 827
(1991).
8. C. B. Yank, C. C. Hsu, Y. S. Park and H. F Shurvell, Eur. Polym. J. 30, 205 (1994).
9. V. K. Gupta and M. Ravindranathan, Polymer 37, 1399 (1996).
10. C. M. Forte and M. B. Coutinho, Eur. Polym. J. 32, 223 (1996).
11. V. K. Gupta Shashikant and M. Ravindranathan, Polym. Plast. Technol. Eng. 36, 167 (1997).
12. T. Garoff, E. Liskola and P. Sormunen, in: Transition Metals and Organometallics as Catalyst for
OleŽ n Polymerization, W. Kaminsky and H. Sinn (Eds), pp. 197– 208. Springer-Verlag, Berlin
(1988).
13. M. C. Sacchi, Z. Q. Fan, F. Forlini, I. Trito and P. Locatelli, Macromol. Chem. Phys. 195, 2805
(1994).
14. M. Härkönen, J. V. Seppälä and T. Vaananen, Makromol. Chem. 192, 721 (1991).
15. M. Härkönen, J. V. Seppälä, R. Chujo and Y. Kohgure, Polymer 36, 1499 (1995).
16. T. J. Burkhardt, A. W. Langer, D. Barist, W. G. Funk and T. Gaydos, in: Transition Metal
Catalyzed Polymerizations, Ziegler–Natta and Metathesis Polymerizations, R. Quirk (Ed),
pp. 227– 239. Cambridge University Press, New York, NY (1988).
17. C. K. Young and W. H. Ray, JMS-Rev. Macromol. Chem. Phys. C25, 57 (1985).