Commercial Methods for the Synthesis of Ziegler-Natta Catalysts for the Production of Polyethylene: A Patent Review

Document Type : compile

Authors

Research and Development Center, Jam Petrochemical Company, Pars Special Economic Energy Zone, Asaluyeh, Bushehr, Iran

Abstract

F or more than sixty years, thousands of patents and articles have been published annually on various manufacturing methods of Ziegler-Natta catalysts and comparing the properties and performance of the obtained catalysts. However, a closer look at these documents reveals that the basic and commercial methods of manufacturing these catalysts may be very limited and that other methods are either not commercializable or are merely subsets of these original methods. In this paper, by reviewing the wide range of numerous patents patented over the past four decades, the main production methods of commercial Ziegler-Natta magnesium-titanium catalysts are categorized based on the morphology of the obtained catalyst. The morphology of Ziegler-Natta catalysts can be divided into two categories: spherical morphology and non-spherical morphology. The morphology of Ziegler-Natta catalysts is one of the most important variables that determines the possibility of using a special catalyst in the polymerization process (gas phase or suspension). Catalysts with spherical morphology can be produced by commercial methods of emulsion, impregnation, and spray drying. In contrast, catalysts with non-spherical morphology can also be produced by commercial methods of reactive precipitation and support conversion

Keywords

References

1.  Jandaghian M.H.,  Soleimannezhad A., Ahmadjo S., Mortazavi S.M.M., and Ahmadi M., Synthesis and Characterization of Isotactic Poly(1-hexene)/Branched Polyethylene Multiblock Copolymer via Chain Shuttling Polymerization Technique, Ind. Eng. Chem. Res., 57, 4807–4814, 2018.
2.  Vyas P.B., Kaur S., Patil H.R., and Gupta V.K., Synthesis of Polypropylene with Varied Microstructure and Molecular Weights Characteristics Using Supported Titanium Catalyst System, J. Polym. Res., 18, 235–239, 2011.
3.  Monji M., Pourmahdian S., Vatankhah M., and Taromi F.A., Synthesis of Highly Improved Ziegler‐Natta Catalyst, J. Appl. Polym. Sci., 112, 3663–3668, 2009.
4.  Albunia A.R., Prades F., and Jeremic D., Multimodal Polymers with Supported Catalysts, Springer, Switzerland, 1-30, 2019.
5. Jamjah R., Zohuri G.H., Vaezi J., Ahmadjo S., Nekomanesh M., and Pouryari M., Morphological Study of Spherical MgCl2. nEtOH Supported TiCl4 Ziegler‐Natta Catalyst for Polymerization of Ethylene, J. Appl. Polym. Sci., 101, 3829–3834, 2006.
6.  Dos Santos B., Dutra C.P., Santos J.H.Z., Fisch A.G., and Cardozo N.S.M., Experimental Evaluation of a Catalyst Fragmentation Model for Olefin Polymerization, Macromol. React. Eng., 14, 2000008-20000014, 2020.
7. Wang D., Yang G., Guo F., Wang J., and Jiang Y., Progress in Technology and Catalysts for Continuous Stirred Tank Reactor Type Slurry Phase Polyethylene Processes, Pet. Chem., 58, 264–273, 2018.
8. Arletti A., Caiazzo L., Collina G., Evangelisti D., Fusco O., and Gaddi B., Magnesium  Dichloride-ethanol Adducts And Catalyst Components Obtained Therefrom, US Pat. 0,014,632, 2005.
9. Collina G., Evangelisti D., Morini G., and Ferrara G., Magnesium Dichloride-Alcohol Adducts and Catalyst Components Obtained Therefrom, WO Pat. 080,568, 2009.
10. Gaddi B., Collina G., and Evangelisti D., Magnesium Dichloride-Alcohol Adducts and Catalyst Components Obtained Therefrom, WO Pat. 095,523, 2014.
11. Kelly M. and Kimberley B.S., Hydrogen Response Through Catalyst Modification, US Pat. 7,671,149, 2010.
12. Jorgensen R.J., Kapur M., Michie W.J., and Wagner B.E., Ethylene-Based Polymer Compositions Methods of Making the Same and Articles Prepared from the Same, WO Pat. 085,922, 2009.
13. Zoeckler M.T., Wagner B.E., and Kao S., Spray-Dried, Mixed Metal Ziegler Catalyst Compositions, US Pat. 7,348,383, 2008.
14. Spriggs T.E., Turner M.D., Wagner B.E., Levandovsky A., and Lacks D.J., Robust Spray-Dried Ziegler-Natta Procatalyst and Polymerization Process Employing Same, WO Pat. 020,623, 2006.
15. Beigzadeh D., Campbell R.E., Ewart S.W., Froese R.D., Jorgensen R.J., and Margl P.M., Self-Limiting Catalyst Composition for Ethylene Polymerization, US Pat. 8,993,692, 2015.
16. Campbell R.E., Chen L., Painter R.B., Reib R.N., and Tilston M.W., Catalyst Composition for Ethylene Polymerization, US Pat. 7,393,910, 2008.
17. Koskinen J. and Jokinen P.A., Polymerization Catalyst Carrier Prepared By Spray Crystallization,  WO Pat. 19,100, 1993.
18. Apecetche M.A., Cao P.A., Awe M.D., Schoed-Wolters A.D., and Impleman R.W., Catalyst Compositions Comprising Small Silica Support Materials and Methods of Use in Polymerization Reactions, US Pat. 7,381,780, 2008.
19. Lalange-Magne C. and Royer-Mladenov C., Process for the Gas-Phase (co-) Polymerisation of Olefins in a Fluidised Bed Reactor, EP Pat. 1,490,415, 2006.
20. Kelly M., Goyal S.K., Ker V., Montyn de Wit P., Kimberley B.S., and Hoang P.P.M., Enhanced Polyolefin Catalyst, US Pat. 7,211,535, 2007.
21. Kelly M. and Kimberley B.S., Hydrogen Response Through Catalyst Modification, US Pat. 7,671,149, 2010.
22. Yasuda K., Matsumoto T., and Mizumoto K., Ultra-high Molecular Weight Polyolefin Fine Particles, Process for Producing the Same and Molded Articles of the Same, US Pat. 0,196,711, 2010.
23. Matsunaga K., Yamamoto H., Yamamoto K., Shinozaki T., and Takahashi K., Solid Titanium Catalyst Component for Ethylene Polymerization, Ethylene Polymerization Catalyst and Ethylene Polymerization Method, US Pat. 8,383,541, 2010.
24. Morini G., Dall’Occo T., Piemontesi F., Spoto R., Vincenzi P., and Vitale G., Process for the Preparation of a Catalyst Component and Components Therefrom Obtained, US Pat. 7,592,286, 2010.
25. Fushimi M., Liguori D., Dall’occo T., Morini G., Pater J.T.M., and Vitale G., Process for the Preparation of Ethylene Polymers with Narrow Molecular Weight Distribution, WO Pat. 015,553, 2011.
26. Fushimi M. and Schneider M., Catalyst for the Polymerization of Olefins, WO Pat. 027,269, 2009.
27. Cermelli I., Dheur L.M.G., and Siberdt F., Polymer Composition for Blow Molding, WO Pat. 178,673, 2013,
28. Berthold J., Heinicke L., and Meier G., Films Having Improved Mechanical Properties, US Pat. 8,673,437, 2014.
29.  Vantomme A., Siraux D., Sinoy A.V., and Gielens J., Bimodal Polyethylene for Blow-Moulding Applications, US Pat. 8,609,792, 2013.
30. Wang S., Liu D., Zhou J., Lü X., Zhang L., and Mao B., Catalyst Component for Polymerization of Olefin and Preparation Method Thereof, US Pat. 9,068,025, 2015.
Basparesh
Volume 11, Issue 2 - Serial Number 39
September 2021
Pages 42-50

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