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A spectroscopic investigation of silica-supported TiClx species: a case study towards Ziegler–Natta catalysis

  • Concepts in catalysis
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Abstract

Since their discovery in the 1950s, several breakthroughs marked the evolution of Ziegler–Natta catalysts and contributed to improve their catalytic activity and selectivity, conditioning the whole polyolefin market. However, some fundamental questions are still open about the structural and functional properties of the active sites, whose understanding could open new perspectives in controlling the polymerization process. In this context, a SiO2-supported Ziegler–Natta catalyst was prepared following a step by step approach, with the simultaneous goal of synthesis and characterization, to investigate with a surface science approach each step of the catalytic process.

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References

  • Albizzati E, Giannini U, Collina G, Noristi L, Resconi L (1996) Catalysts and polymerizations. In: Moore EPJ (ed) Polypropylene Handbook. Hanser-Gardner Publications, Cincinnati, Chapter 2

  • Bamoniri A, Mirjalili BBF, Tarazian R (2015) Nano-TiCl4/SiO2: an efficient heterogeneous solid acid catalyst for the one pot cascade five-component synthesis of densely functionalized tetrahydropyridines. J Chem Sci 127(5):885–895

  • Benn R, Janssen E, Lehmkuhl H, Rufínska A (1987) 27Al-NMR-Spektroskopie zur Charakterisierung von Organoaluminium-Verbindungen. J Organomet Chem 333(2):155–168

  • Blaakmeer ES, Antinucci G, Busico V, Van Eck ERH, Kentgens APM (2016) Solid-state NMR investigations of MgCl2 catalyst support. J Phys Chem C 120(11):6063–6074

  • Busico V, Causa M, Cipullo R, Credendino R, Cutillo F, Friederichs N, Lamanna R, Segre A, Castellit VV (2008) Periodic DFT and high-resolution magic-angle-spinning (HR-MAS) H-1 NMR investigation of the active surfaces of MgCl2-supported Ziegler-Natta catalysts. The MgCl2 matrix. J Phys Chem C 112(4):1081–1089

  • Busico V, Cipullo R, Mingione A, Rongo L (2016) Accelerating the research approach to Ziegler-Natta catalysts. Ind Eng Chem Res 55(10):2686–2695

  • Chang M, Liu X, Nelson PJ, Munzing GR, Gegan TA, Kissin YV (2006) Ziegler-Natta catalysts for propylene polymerization: Morphology and crystal structure of a fourth-generation catalyst. J Catal 239(2):347–353

  • Chelazzi D, Ceppatelli M, Santoro M, Bini R, Schettino V (2004) High‐pressure synthesis of crystalline polyethylene using optical catalysis. Nat Mater 3(7):470–475

  • Clark RJH (1964) Diffuse reflectance spectra of some anhydrous transition-metal halides. J Chem Soc 417–425

  • Corradini P, Guerra G, Cavallo L (2004) Do new century catalysts unravel the mechanism of stereocontrol of old Ziegler-Natta catalysts? Acc Chem Res 37(4):231–241

  • Crouch PC, Fowles GWA, Walton RA (1969) Complex halides of transition metals. Part X. Reaction of molten diethylammonium chloride with titanium(III), vanadium(III), and chromium(III) chlorides: a spectroscopic and magnetic study of the TiCl6 3−, Ti2Cl9 3−, V2Cl9 3−, and Cr2Cl9 3− anions. J Chem Soc A 972–976

  • D’Amore M, Thushara KS, Piovano A, Causà M, Bordiga S, Groppo E (2016) Surface investigation and morphological analysis of structurally disordered MgCl2 and MgCl2/TiCl4 Ziegler–Natta catalysts. ACS Catal 6(9):5786–5796

  • Duffy JA (1977) Variable electronegativity of oxygen in binary oxides: possible relevance to molten fluorides. J Chem Phys 67(6):2930–2931

  • Fink G, Steinmetz B, Zechlin J, Przybyla C, Tesche B (2000) Propene polymerization with silica‐supported metallocene/MAO catalysts. Chem Rev 100:1377–1390

  • Ghiotti G, Garrone E, Morterra C, Boccuzzi F (1979) Infrared study of low temperature adsorption. 1. CO on Aerosil. An interpretation of the hydrated silica spectrum. J Phys Chem 83(22):2863–2869

  • Groppo E, Lamberti C, Bordiga S, Spoto G, Zecchina A (2005) The structure of active centers and the ethylene polymerization mechanism on the Cr/SiO2 catalyst: a frontier for the characterization methods. Chem Rev 105:115–183

  • Groppo E, Seenivasan K, Barzan C (2013) The potential of spectroscopic methods applied to heterogeneous catalysts for olefin polymerization. Catal Sci Technol 3:858–878

  • Jorgensen CK (1962) Electronegativity and chemical bonding. Orbitals in atoms and molecules, Academic Press, London and New York, vol 7, pp 80–100

  • Jorgensen CK (1970) Electron transfer spectra. Progr Inorg Chem 12:101–157

  • Joustra AH, De Bruijn W, Drent E, Reman WG (1989) A process for the preparation of an oxirane compound. EP0345856

  • Kaminsky W (1996) New polymers by metallocene catalysis. Macromol Chem Phys 197(12):3907–3945

  • Kaminsky W, Winkelbach H (1999) Influence of supported metallocene catalysts on polymer tacticity. Top Catal 7(1–4):61–67

  • Kerber RN, Kermagoret A, Callens E, Florian P, Massiot D, Lesage A, Coperet C, Delbecq F, Rozanska X, Sautet P (2012) Nature and structure of aluminum surface sites grafted on silica from a combination of high-field aluminum-27 solid‐state NMR spectroscopy and first-principles calculations. J Am Chem Soc 134(15):6767–6775

  • Kinney JB, Staley RH (1983) Reactions of titanium tetrachloride and trimethylaluminum at silica surfaces studied by using infrared photoacoustic spectroscopy. J Phys Chem 87:3735–3740

  • Klapper M, Joe D, Nietzel S, Krumpfer JW, Müllen K (2014) Olefin polymerization with supported catalysts as an exercise in nanotechnology. Chem Mater 26(1):802–819

  • Kvisle S, Rytter E (1984) Infrared matrix isolation spectroscopy of trimethylgallium, trimethylaluminium and triethylaluminium. Spectrochim Acta A 40(10):939–951

  • Liu T, Li W, Xia X, Mao B (2015) Study of a novel fourth-generation supported Ziegler-Natta catalyst for propylene polymerization: Relationship between catalyst structure and polymerization properties. China Pet Process Pe. 17(1):39–47

  • McGrady GS (2000) Structure of the trimethylaluminum dimer as determined by powder neutron diffraction at low temperature. Organometallics 19(21):4398–4401

  • Mirjalili BBF, Bamoniri A, Zamania L (2012) Nano-TiCl4/SiO2: an efficient and reusable catalyst for the synthesis of tetrahydrobenzo[a]xanthenes-11-ones. Lett Org Chem 9(5):338–343

  • Mirjalili BBF, Zamani L, Afr S (2014) Nano-TiCl4/SiO2: a versatile and efficient catalyst for synthesis of dihydropyrimidones via biginelli condensation. J Chem 67:21–26

  • Morra E, Giamello E, Van Doorslaer S, Antinucci G, D’Amore M, Busico V, Chiesa M (2015) Probing the coordinative unsaturation and local environment of Ti3+ sites in an activated high-yield ziegler-natta catalyst. Angew Chem Int Ed 54(16):4857–4860

  • Muddada NB, Olsbye U, Fuglerud T, Vidotto S, Marsella A, Bordiga S, Gianolio D, Leofanti G, Lamberti C (2011) The role of chlorine and additives on the density and strength of Lewis and Bronsted acidic sites of gamma-Al2O3 support used in oxychlorination catalysis: A FTIR study. J Catal 284(2):236–246

  • Nowlin TE, Mink RI, Lo FY, Kumar T (1991) Ziegler-Natta catalysts on silica for ethylene polymerization. J Polym Sci Part A Polym Chem 29(8):1167–1173

  • Olabisi O, Atiqullah M, Kaminsky W (1997) Group 4 metallocenes: supported and unsupported. J Macromol Sci Rev Macromol Chem Phys 37(3):519–554

  • Piovano A, Thushara KS, Morra E, Chiesa M, Groppo E (2016) Unraveling the catalytic synergy between Ti3+ and Al3+ sites on a chlorinated Al2O3: a tandem approach to branched polyethylene. Angew Chem Int Ed 55(37):11203–11206

  • Pullukat TJ, Hoff RE (1999) Silica-based Ziegler-Natta catalysts: a patent review. Catal Rev Sci Eng 41(3–4):389–428

  • Robert C, Thomas CM (2013) Tandem catalysis: a new approach to polymers. Chem Soc Rev 42(24):9392–9402

  • Schrijnemakers K, Van Der Voort P, Vansant EF (1999) Characterization of a TiCl4-modifed silica surface by means of quantitative surface analysis. Phys Chem Chem Phys 2569–2572

  • Seenivasan K, Sommazzi A, Bonino F, Bordiga S, Groppo E (2011) Spectroscopic investigation of heterogeneous Ziegler-Natta catalysts: Ti and Mg chloride tetrahydrofuranates, their interaction compound, and the role of the activator. Chem Eur J 17(31):8648–8656

  • Sormunen P, Hjertberg T, Iiskola E (1990) A solid-state 13C NMR study on heterogeneous Ziegler-Natta catalyst components. Makromol Chem 191(11):2663–2673

  • Terano M (2004) Current achievements on heterogeneous olefin polymerization catalysts. Sankeisha & Co., Ltd, Nagoya

  • Tisse VF, Boisson C, McKenna TFL (2014) Activation and deactivation of the polymerization of ethylene over rac-EtInd2ZrCl2 and (nBuCp)2ZrCl2 on an activating silica support. Macromol Chem Phys 215(14):1358–1369

  • Wang J, Wang L, Gao H, Wang W, Zhao Z, Sun T, Feng L (2006) Ethylene polymerization using a novel MgCl2/SiO2-supported Ziegler-Natta catalyst. Polym Int 55(3):299–304

  • Xu MC, Noei H, Fink K, Muhler M, Wang YM, Woll C (2012) The surface science approach for understanding reactions on oxide powders: The importance of IR spectroscopy. Angew Chem Int Ed 51(19):4731–4734

  • Zecchina A, Otero Areán C (1996) Diatomic molecular probes for mid‐IR studies of zeolites. Chem Soc Rev 25:187–197

  • Zecchina A, Spoto G, Bordiga S, Padovan M, Leofanti G, Petrini G (1991) IR Spectra of CO adsorbed at low temperature (77 K) on Titaniumsilicalite, H-ZSM5 and Silicalite. Stud Surf Sci Catal 65:671–680

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Acknowledgements

We are grateful to Elena Groppo, Silvia Bordiga and Adriano Zecchina for their inspiring guidance in the field of polymerization catalysis. This work has been supported by the Progetto di Ateneo/CSP 2014 (Torino_call2014_L1_73).

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Authors and Affiliations

  1. Department of Chemistry, NIS Centre and INSTM, University of Torino, via Quarello 15A, 10135, Turin, Italy

    Alessandro Piovano, Giorgia A. Martino & Caterina Barzan

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  1. Alessandro Piovano
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  2. Giorgia A. Martino
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  3. Caterina Barzan
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Correspondence to Alessandro Piovano.

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Piovano, A., Martino, G.A. & Barzan, C. A spectroscopic investigation of silica-supported TiClx species: a case study towards Ziegler–Natta catalysis. Rend. Fis. Acc. Lincei 28 (Suppl 1), 43–49 (2017). https://doi.org/10.1007/s12210-016-0582-y

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