Ziegler-Natta catalysts for propylene polymerization – Interaction of an external donor with the catalyst

Document Type : Original research


1 Boreskov Institute of Catalysis SB RAS, Prospekt Akad. Lavrentieva 5, 630090, Novosibirsk, Russian Federation

2 Novosibirsk State University, Pirogova Str. 2, 630090, Novosibirsk, Russian Federation


The interaction of the external donor (propyltrimethoxysilane - PTMS) with titanium-magnesium catalysts (TMCs) containing dibutylphthalate (DBP) as internal donor, which were prepared in different ways, was studied by chemical analysis and infrared diffuse reflectance spectroscopy (DRIFTS). The chemical composition of the catalysts after their interaction with heptane solutions of PTMS, PTMS/AlEt3 or AlEt3 during 1h at 70°C showed that this interaction led to removal of both TiCl4 and DBP from the catalysts. The fractions of DBP and Ti extracted, as well as the amounts of PTMS and AlEt3 bound, depended on the method of synthesizing the catalysts. DRIFT spectroscopy data concerning the state of DBP in the catalysts, before and after treatment with heptane solutions of PTMS or PTMS/AlEt3 during 1h at 70°C, showed that PTMS could substitute both TiCl4 and DBP, while adsorbing on coordinatively unsaturated Ti and Mg ions in the catalyst. The presence of AlEt3 played a key role in the interaction of PTMS with the catalyst. Activity data for propylene polymerization showed that treatment of TMC catalysts with PTMS before polymerization led to a sharp activity decrease due to deactivation of active sites, while the interaction of the catalyst with PTMS in the presence of AlEt3 led only to a slight decrease of activity, probably due to deactivation of non-stereospecific active centers.


Main Subjects

  1. Soga K, Shiono T, Doi Y (1988) Influence of internal and external donors on activity and stereospecificity of Ziegler-Natta catalysts. Makromol Chem 189: 1531-1541
  2. Yang СB, Hsu CC, Park YS, Shurvell HF (1994) Infrared characterization of MgCl2 supported Ziegler-Natta catalysts with monoester and diester as a modifier. Eur Polym J 30(2): 205-214
  3. Arzoumanidis GG, Karayannis NW (1991) Infrared spectral characterization of supported propene polymerization catalysts. A link to catalyst performance. Appl Catal 76: 221-231
  4. Panchenko VN, Goryachev AN, Vorontsova LV, Paukshtis EA, Zakharov VA (2014) Basicity of stereoregulating electron-donor compounds in Ziegler−Natta catalysts: A study by infrared spectroscopy and chemical exchange reactions. J Phys Chem C 118: 28572−28579
  5. Potapov AG, Bukatov GD, Zakharov VA (2009) DRIFTS study of the interaction of the AlEt3 cocatalyst with the internal donor ethyl benzoate in supported Ziegler–Natta catalysts. J Mol Catal A-Chem 301: 18–23
  6. Makwana U, Naik DG, Singh G, Patel V, Patil HR, Gupta VK (2009) Nature of phthalates as internal donors in high performance MgCl2 supported titanium catalysts. Catal Lett 131: 624–631
  7. Shen X-R, Fu Z-S, Hu J, Wang Q, Fan Z-Q (2013) Mechanism of propylene polymerization with MgCl2-supported Ziegler−Natta catalysts based on counting of active centers: The role of external electron donor. J Phys Chem C 117: 15174−15182
  8. Terano M, Kataoka T, Keii T (1990) Analytical and kinetic approaches for the basic type of MgCl2,-supported high yield catalysts. J Polym Sci Pol Chem 28: 2035-2048
  9. Cheruvathur AV, Langner EHG, Niemantsverdriet JWH, Thüne PC (2012) In situ ATR-FTIR studies on MgCl2-diisobutyl phthalate interactions in thin film Ziegler-Natta catalysts. Langmuir 28: 2643- 2651
  10. Chadwick JC (2001) advances in propene polymerization using MgCl2-supported catalysts. Fundamental aspects and the role of electron donors. Macromol Symp 173: 21–35
  11. Credendino R, Liguori D, Morini G, Cavallo L (2014) Investigating phthalate and 1,3-diether coverage and dynamics on the (104) and (110) surfaces of MgCl2 supported Ziegler−Natta catalysts. J Phys Chem C 118: 8050-8058
  12. Stukalov DV, Zilberberg IL, Zakharov VA (2009) Surface species of titanium(IV) and titanium(III) in MgCl2-supported Ziegler−Natta catalysts. A periodic density functional theory study. Macromolecules 42: 8165–8171
  13. Stukalov DV, Zakharov VA, Potapov AG, Bukatov GD (2009) Supported Ziegler–Natta catalysts for propylene polymerization. Study of surface species formed at interaction of electron donors and TiCl4 with activated MgCl2. J Catal 266: 39-49
  14. Bazhenov AS, Denifl P, Leinonen T, Pakkanen A, Linnolahti M, Pakkanen TA (2014) Modeling coadsorption of titanium tetrachloride and bidentate electron donors on magnesium dichloride support surfaces. J Phys Chem C 118: 27878-27883
  15. Busico V, Causa M, Cipullo R, Credendino R, Cutillo F, Friederichs N, Lamanna R, Segre A, Van Axel Castelli V (2008) Periodic DFT and high-resolution magic-angle-spinning (HR-MAS) 1H NMR investigation of the active surfaces of MgCl2-supported Ziegler-Natta catalysts. The MgCl2 matrix. J Phys Chem C 112(4): 1081-1089
  16. Liu B, Nitta T, Nakatani H, Terano M (2004) Precise arguments on the distribution of stereospecific active sites on MgCl2-supported Ziegler-Natta catalysts. Macromol Symp 213: 7-18
  17. Noristi L, Barbe’ PC, Baruzzi G (1991) Effect of the internal-externa1 donor pair in high-yield catalysts for propylene polymerization. 1. Catalyst-cocatalyst interactions. Makromol Chem 192: 1115-1127
  18. Seppälä JK, Harkonen M, Luciani L (1989) Effect of the structure of external alkoxysilane donors on the polymerization of propene with high activity Ziegler-Natta catalysts. Makromol Chem 190: 2535-2550
  19. Proto A, Oliva L, Pellecchia C, Sivak AJ, Cullo LA (1990) Isotactic-specific polymerization of propene with supported catalysts in the presence of different modifiers. Macromolecules 23: 2904- 2907
  20. Pakkanen TT, Vahasarja E, Pakkanen TA, Iiskola E (1990) Modification of olefin polymerization catalysts. III. A 13C CP-MAS NMR study of adsorption of silyl ethers on MgCI2-supported Ziegler-Natta catalysts. J Catal 121: 248-261
  21. Chumachenko NN, Zakharov VA, Bukatov GD, Sergeev SA (2014) A study of the formation process of titanium–magnesium catalyst for propylene polymerization. Appl Catal A-Gen 469: 512– 516
  22. Makhtarulin SI, Moroz EM, Vermel EE, Zakharov VA (1978) Influence of the substructure of supported titanium-magnesium catalysts on their activity in olefin polymerization. React Kinet Catal Lett 9(3): 269-274
  23. Boero M, Parrinello M, Weiss H, Hu1ffer S (2001) A first principles exploration of a variety of active surfaces and catalytic sites in Ziegler- Natta heterogeneous catalysis. J Phys Chem A 105: 5096-5105
  24. Chumachenko NN, Bukatov GD, Sergeev SA, Zakharov VA (2011) State of titanium in supported titanium-magnesium catalysts for propylene polymerization. Kinet Catal+ 52: 234-241
  25. Potapov AG, Terskikh VV, Bukatov GD, Zakharov VA (2000) 27Al MAS NMR study of the interaction of supported Ziegler–Natta catalysts with organoaluminium co-catalyst in the presence of donors. J Mol Catal A-Chem 158: 457–460
  26. Sacchi MC, Forlini F, Tritto I, Locatelli P (1996) Polymerization stereochemistry with Ziegler- Natta catalysts containing dialkylpropane diethers: A tool for understanding internal/ external donor relationships. Macromolecules 29: 3341-3345
  27. Sacchi MC, Tritto I, Shan C, Mendichi R, Noristi L (1991) Role of the pair of internal and external donors in MgCl2-supported Ziegler-Natta catalysts. Macromolecules 24: 6823-6826
  28. Noristi L, Barbe PC, Baruzzi G (1991) Effect of the internal/external donor pair in high-yield catalysts for propylene polymerization, catalyst-cocatalyst interactions. Makromol Chem 192: 1115-1127
  29. Capone F, Rongo L, D’Amore M, Budzelaar PHM, Busico V (2013) Periodic hybrid DFT approach (including dispersion) to MgCl2 supported Ziegler−Natta catalysts. 2. Model electron donor adsorption on MgCl2 crystal surface. J Phys Chem C 117: 24345−24353
Volume 4, Issue 1 - Serial Number 7
January 2017
Pages 87-97
  • Receive Date: 14 June 2016
  • Revise Date: 22 August 2016
  • Accept Date: 08 September 2016
  • First Publish Date: 01 January 2017