The Catalyst Review June 2019 - 11

SPECIAL FEATURE
Advantages of the Organometallic Complex Coordinated on MgCl2
The immediate advantage of the new catalysts is a polymerization activity increase of up to 60% compared with the standard DBP
catalyst. It has also been observed that the charge of the DMS ED could be reduced by about 30%, without any detrimental effect.
From this observation, we may assume that the ED does not affect the complex IV active site.
Using a combination of MgCl2 supported catalysts incorporating organometallic complexes like the IV as IDs, with ligands like PHIND
as EDs we may increase synergistically the activity of the system up to 100%. One important advantage of this catalytic system is the
activation with simple alkyls like TEA, unlike the metallocenes and post-metallocenes that are activated with MAO.
Besides the catalytic activity improvement of catalyst incorporating organometallic complexes like IV, the xylene solubles of the
polymer produced are less than 2%, and the powder bulk density is usually higher by about 10%. There have been also changes in
the hydrogen response of such catalysts, and other property improvements. A thorough study has not been conducted in this area.
Closing Remarks
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A Ti organometallic polymerization catalyst coordinated (supported) on MgCl2 is a novel finding, with several commercial
and scientific implications.
The technology can be easily applied to existing commercial systems, since the activator (TEA) remains the same.
In our catalyst preparation we utilize a soluble complex II, which at an elevated temperature converts into an insoluble
complex IV. This is very advantageous in catalyst manufacturing.
PHIND is only one example of a ligand capable of undergoing orthometallation with TiCl4 and ZrCl4, improving MgCl2
supported catalyst performance. We have successfully worked with many other ligands showing similar or even better
performance.
The possibility exists to develop a single-site MgCl2 supported polymerization catalyst if we succeed in introducing complex
IV as the only active site (Arzoumanidis 2015). The obvious advantages of such development would be production of
metallocene-like polymers by every commercial plant.

References

Albizzati E, Giannini U, Morini G, et al. (1995). "Advances in Propylene Polymerization with MgCl2 Supported Catalysts." In Fink G,
Malhaupt R, Brinntzinger H, (Eds), Ziegler Catalysts: Springer 1995, p. 413.
Arzoumanidis GG. (2015). "Novel Single Site Z-N Catalyst Development." Presented at 'Advances in Polyolefins 2015,' PolyACS,
Sonoma Valley, California: DOI:10.13140/RG.2.2.32676.37769.
Arzoumanidis GG. (2014). "Amoco CD Commercial Polypropylene Catalyst, Tailored-made for the Amoco-Chisso Gas Phase Process."
Polyolefins Journal, 1(2): 131-137.
Bukatov GD, Maslov DK, Sergeev SA, Matsko MA. (2019). "Effect of Internal Donord on the Performance of Ti-Mg Catalysts in
Propylene Polymerization: Donor Introduction During or After Mgcl2 Formation." Applied Catalysis A, General, 577: 69-75.
Groppo E, Seenivasan K, Barzan C. (2013). "The Potential of Spectroscopic Methods Applied to Heterogeneous Catalysts for Olefin
Polymerization" Catal.Sci.Technol., 3: 858. https://pubs.rsc.org/en/content/articlehtml/2013/cy/c2cy20559a
Stukalov DV, Zakharov VA, Potapov AG, Bukatov GB. (2009). "Supported Ziegler-Natta Catalysts for Propylene Polymerization. Study of
Surface Species Formed at Interaction of Electron Conors and TiCl4 With Activated MgCl2." Journal of Catalysis, 266(1): 39-49.
About the Author

Gregory G. Arzoumanidis is an International Consultant in commercial polyolefin catalysts. While at Amoco
Chemicals he was the principal investigator for the development of the Amoco CD catalyst, now produced
commercially and used by more than two dozen PP plants. His present focus is on new cyclometallated complexes
of Ti and Zr invented by him, which may provide polymer product advantages, when incorporated in existing
commercial catalyst systems. Dr. Arzoumanidis can be reached at arzoumandis@gmail.com.

The Catalyst Review

June 2019

https://pubs.rsc.org/en/content/articlehtml/2013/cy/c2cy20559a

The Catalyst Review June 2019

Table of Contents for the Digital Edition of The Catalyst Review June 2019