Tailoring polypropylene properties by package of internal/external donor in Ziegler Natta catalysts

Document Type : Original research

Authors

1 National Petrochemical Company-Research & Technology Co. (NPC-RT), Tehran, Iran

2 Department of Catalyst, Iran Polymer & Petrochemical Institute, Tehran, Iran

Abstract

Insights have been developed into the influence of different structures, including bismethoxymethylfluorene (B) and 2,2-diisopropyl succinate (I), on both internal donor (ID) and external donor (ED) roles on the performance of MgCl2/ID/TiCl4. Catalyst performance including activity, hydrogen response, molecular weight distribution and thermal properties is explained through the coordination nature of external donors and its correlation with the internal donor. Replacement of the typical alkoxysilane ED with B and I leads to an overall decrease in activity, which is more pronounced (average 1.4 times) in systems with similar structures as ID and ED. However, these compounds significantly enhance hydrogen response. The use of B as ED leads to an average 1.5-fold increase in MFI and usage of I as ED results in an average 1.1 times increase in MFI. Changing the ED influenced the thermal properties so that in the catalyst with the succinate structure as ID, altering the ED from alkoxysilane to I, leads to an increase in crystallinity from 43.86% to 48.12%. These findings suggest that the choice of package of internal and external donor can significantly influence the resulting polymer characteristics.
 

Keywords

Main Subjects


  1. Hadian N, Nekoomanesh-Haghighi M, Bahri-Laleh N (2014) Storage time effect on dynamic structure of MgCl2.nEtOH adducts in heterogeneous Ziegler Natta cataltsts. Polyolefins Journal 1: 33-41 [CrossRef]
  2. Zhang J, Nan F, Yu H, Zhang S, Xia X., Huang Q, Yi J, Li H, Zho Z (2020) Direct preparation of transparent isotactic polypropylene with supported Ziegler Natta catalysts containing novel eco-friendly electron donors.  Ind Eng Chem Res 59: 8995−9003 [CrossRef]
  3. Nouri Ahangarani F, Bahri-Laleh N, Nekomanesh-Haghigh M (2016) The use of electron donors to increase stereospecificity in Ziegler Natta catalyzed propylene polymerization: J Iran Polym Sci Technol 29: 105−125 [CrossRef]
  4. Busico V, Causà M, Cipullo R, Credendino R, Cutillo F, Friederichs N, Lamanna R, Segre A, Castelli VVA (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: 1081-1089 [CrossRef]
  5. Zhang H, Lee YJ, Park JR, Lee DH, Yoon KB (2011) Control of molecular weight distribution for polypropylene obtained by commercial Ziegler-Natta catalyst: Effect of electron donor. Macromol Res19: 622-628 [CrossRef]
  6. Fushimi M, Guidotti S, Oliver Kristen M, Mignogna A, Morini G, Paterus JTM (2013) Catalyst systems for the polymerization of olefins. US20130102744
  7. Ghasemi Hamedani N, Arabi H, Poorsank F (2020) Towards the design of mixture of diether and succinate as internal donor in MgCl2 supported Ziegler Natta catalyst: New J Chem 44: 15758-15768 [CrossRef]
  8. Ghasemi Hamedani N, Arabi H, Poorsank F (2021) Propylene polymerization with MgCl2/Mixed-IDs/TiCl4 system in the presence of different external donor structures. J Polym Res 28: 418 [CrossRef]
  9. Sainani J (2018) Process for the synthesis of 9,9-bis(methoxymethyl)fluorine. US 10081586B2
  10. Xie L Tian Y, Feng Z, Zhao S, Kang Y, Sun Z (2011) Process for preparing 2,3-di-non-straight-alkyl-2-cyano succinic acid diesters. EP 2399902 A1
  11. Mehdizadeh M, Karkhaneh F, Nekomnanesh M, Sadjadi S, Emami M, Teimoury H, Salimi M, Sola M, Poater A, Bahri-Laleh N (2023) Influence of the ethanol content of adduct on the comonomer incorporation of related Ziegler Natta catalysts in propylene (co)polymerization. Polymers 15: 15234476 [CrossRef]
  12. Cho HS, Lee WY (2003) Synthesis of inorganic MgCl2 alcohol adduct via recrystallization method and its application in supported organometallic catalysts for the polymerization of ethylene with 1-hexene. J Mol Catal-A 191: 155-165 [CrossRef]
  13. Poorsank F, Arabi H, Ghasemi Hamedani N (2019) Silyl diol ester as a new selectivity control agent in MgCl2-supported Ziegler–Natta systems for propylene polymerization: catalyst structure and polymer properties. RSC Adv 9: 7420-7431 [CrossRef]
  14. Moore EP (1996) Polypropylene Handbook: Polymerization, characterization, properties, processing, application, Hanser Publishers
  15. Wen X, Ji M, Yi Q, Niu H, Dong JY (2010) Magnesium chloride supported Ziegler-Natta catalysts cntaining succinate internal electron donors for the polymerization of propylene. J Appl Polym Sci 118: 1853-1858 [CrossRef]
  16. Singh G, Kaur S, Makwana U, Patankar RB, Gupta VK (2009) Influence of internal donors on the performance and structure of MgCl2 supported titanium catalysts for propylene polymerization. Macromol Chem Phys 210: 69-76 [CrossRef]
  17. Taniike T, Terano M (2012) Coadsorption model for first-principle description of roles of donors in heterogeneous Ziegler-Natta propylene polymerization. J Catal 293: 39–50 [CrossRef]
  18. Shen XR, Fu ZS, Hu J, Wang Q, Fan ZQ (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 [CrossRef]
  19. Chadwick JC (2007) Advances in propene polymerization using MgCl2‐supported catalysts. Fundamental aspects and the role of electron donors. Macromol Symp 173: 21–36 [CrossRef]
  20. 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 [CrossRef]
  21. Liu BP, Nitta T, Nakatani H, Terano M (2004) Precious arguments on the distribution of stereospecific active sites on MgCl2 supported Ziegler Natta catalysts. Macromol Symp 213: 7−18 [CrossRef]
  22. Chadwick JC, Van Kessel GMM, Sudmeijer O (1995) Regio and stereospecificity in propene polymerization with MgCl2 supported Ziegler Natta catalysts: Effect of hydrogen and external donor. Macromol Chem Phys 196, 1431-1437 [CrossRef]
  23. Zhou Q, Wang A, Li H, Luo Z, Zheng T, Zhang L, Hu Y (2016) Microstructure of polypropylene and active center in Ziegler-Natta catalyst: effect of novel salicylate internal donor. RSC Adv 6: 75023-75031 [CrossRef]   
  24. Potapov AG, Bukatov GD, Zakharov VA (2010) DRIFTS study of the interaction of the Internal donor in TiCl4 di-n-butyl phthalate/MgCl2 catalysts with AlEt3 cocatalyst. J Mol Catal-A 316: 95-99 [CrossRef]
  25. Yaluma AK, Tait PJ, Chadwick JC (2006) Active center determinations on MgCl2-supported fourth- and fifth-generation Ziegler–Natta catalysts for propylene polymerization. J Polym Sci Pol Chem 44: 1635-1647 [CrossRef]
  26. Correa A, Credendino R, Pater JT, Morini G, Cavallo L (2012) Theoretical investigation of active sites at the corners of MgCl2 crystallites in supported Ziegler-Natta catalysts. Macromolecules 45: 3695-3701 [CrossRef]
  27. Hu Y, Chien JCW (1988) Superactive and stereospecific catalysts. I. Structures and productivity. J Polym Sci Pol Chem 26: 2003-2018 [CrossRef]
  28. Di Noto V, Bresadola S (1996) New synthesis of a highly active δ‐MgCl2 for MgCl2/TiCl4/AlEt3 catalytic systems. Macromol Chem Phys 197: 3827-3835 [CrossRef]
  29. Chadwick JC, Van Der Burgt FP, Rastogi S, Busico V, Cipullo R, Talarico G, Heere JJ (2004) Influence of Ziegler-Natta catalyst regioselectivity on polypropylene molecular weight distribution and rheological and crystallization behavior. Macromolecules 37: 9722-9727 [CrossRef]
Volume 11, Issue 4 - Serial Number 26
December 2024
Pages 255-263
  • Receive Date: 06 October 2024
  • Revise Date: 05 November 2024
  • Accept Date: 06 November 2024
  • First Publish Date: 10 November 2024