Surface investigation of the active sites in MgCl2 supported

Ziegler-Natta catalysts by in-situ FTIR spectroscopy

K.S. Thushara*, A. Piovano, E. Groppo and S. Bordiga
Dipartimento di Chimica, NIS Centre and INSTM, Universit di Torino,
Via Quarello, 15,10135, Torino, Italy.
(*) Corresponding Author: thushara.thushara@unito.it
Introduction:
MgCl2 supported Ziegler-Natta (Z-N) catalysts for
the polymerizations of olefins have had spectacular
success in simplifying the polymerization process and
improving polymer quality.
Identification of active site is one of the challenging
problems in supported Z-N systems due to the
hygroscopic nature, oxygen affinity and low content of
active sites.
Investigation of surface adsorption sites in both the
active MgCl2 support and the MgCl2/TiCl4 (Z-N) Goal:
catalysts can provide an opportunity to correlate the The present work deals a characterization of the surface sites present on different MgCl2
surface structure and the catalytic activity in olefin samples and corresponding titanated MgCl2 pre-catalysts, by in-situ FTIR spectroscopy
polymerization. using CO as a probe molecule.
Methods: Active MgCl2 supports were prepared by chemical methods, starting from MgCl2-alcohol adducts; among aliphatic alcohols, methanol and ethanol
were chosen. Titanation, which was achieved by interaction with TiCl4, either from vapour or liquid phase, preferentially involves the exposed surface where Mg
2+ cations are 4-fold coordinated.

MgCl2 Structural and Surface Characterization

FT-IR spectroscopy of adsorbed CO gives indication on the relative proportion of the
exposed (104) and (110) faces, respectively.

Two IR absorption bands are observed upon CO adsorption at 100 K, whose position is a
function of the CO coverage. These two bands are assigned to CO adsorbed through the C end on
Mg2+ sites 5-coordinated and 4-coordinated, respectively.

MgCl2 obtained from dealcoholation of MgCl2-nROH adducts display a higher fraction of Mg4c
sites, i.e. (110) surface is larger than (104) surface. In other words, the alcohol stabilizes the (110)
surface with respect to the (104) one. This is in agreement with literature findings: in the absence of
any Lewis basis, such as in the simple mechanical milling of MgCl2, it is expected to have large
crystallites presenting (104) edges, whereas in the presence of a Lewis basis, smaller crystallites
presenting (110) edges should be formed.
MgCl2 exhibits rhombohedral structure In situ FT-IR study of CO adsorbed at 100K
with cubic close packing giving characteristic
MgCl2(Aldrich)@250C MgCl2-nEtOH@250C MgCl2-6MeOH (AD)@200C MgCl2-nMeOH (DR)@200C
XRD pattern at 2 = 15.10 (003) 350 (004), Mg4c Mg5c Mg4c Mg5c Mg4c Mg5c Mg4c Mg5c
and 50.40(110).
Absorbance (a.u.)

Absorbance (a.u.)

Absorabance

0.1
Absorbance (a.u.)

0.1 0.1
The high intense peak in MgCl2-nROH at
2 < 150 indicates the insertion of ROH in 0.2

between the Cl-Mg-Cl layer of MgCl2.

Dealcoholation results disordered MgCl2
structure.
MgCl2/TiCl4 Structural and Surface Characterization
At room temperature, TiCl4 is mostly
physisorbed on all the MgCl2 samples. The
more evident absorption band at 822 cm-1 is
easily reversible upon degassing at room
temperature.
A heating (and degassing) step at mild
temperature (60-80C) eliminates the
physisorbed TiCl4. The IR spectra of the
titanated samples show a weak and broad
absorption band around 800-900 cm-1,
which could be related to grafted TiClx
species.
References:
1. S.H. Kim, C.R. Tewell, G.A. Somorjai ,
Langmuir, 2000, 16, 9414.
2. D. V. Stukalov and V. A. Zakharov et al. J.
Phys. Chem. C 2009, 113, 21376.
3. E.Groppo, K. Seenivasana, C. Barzan,
Catal. Sci. Technol., 2013, 3, 858.
2200 2190 2180 2170 2160 2150 2140
2200 2190 2180 2170 -1 2160 2150 2140
Wavenumber(cm )
2200 2190 2180 2170 2160 2150 2140
-1
Wavenumber (cm )
2200 2190 2180 2170 2160 2150 2140
-1
Wavenumber(cm )
-1
Wavenumber (cm )
CO adsorption at 100 K on titanated catalysts shows that
TiCl4 interacts mainly with the 4-coordinated Mg2+ sites of
the (110) face.
4. K.S. Thushara, E. S. Gnanakumar, R. Jha, Conclusions:
R. Mattew, T. G. Ajithkumar, P. R. Studies shows that CO is a good probe molecule to investigate
Rajamohanan, K. Sarma, S. Bhaduri, C. S. the surface sites present on the both MgCl2 support and titanated
Gopinath , J. Phys. Chem. C, 2011, 115, 1952. catalyst by in-situ FTIR spectroscopy.
The nature of the active sites exposed is vary with MgCl2 supports
prepared from different alcoholic adduct.