Characterization of phthalate internal donor in MgCl2 supported Ziegler-Natta catalyst by solid state 13C NMR

Document Type : Original research

Authors

1 Research and Development Division, Toho Titanium Co., LTD., 3-3-5, Chigasaki Chigasaki-City, Kanagawa, 253-8510, Japan

2 Professor Emeritus at Tokyo Institute of Technology, 2-12-1, Ookayama Meguro-ku, Tokyo, 152-8550, Japan

Abstract

Ziegler-Natta catalyst for propylene polymerization, which TiCl4 and di-alkyl phthalate were supported on MgCl2, was analyzed by solid state 13C NMR. It was confirmed that the spin-lattice relaxation time (“relaxation time” hereafter) of carbonyl group in phthalate was shortened with increasing measurement temperature as a general manner because of the enhancing of molecular mobility at high temperature. The degree of the relaxation period reduction with temperature was influenced by the alkyl group size in phthalate molecule; the larger alkyl group showed a greater shorting of the relaxation period. A short relaxation time should suggest a weak interaction between the phthalate molecule and the MgCl2 support surface. The change in catalytic performance was discussed by the active site formation mechanism involving the phthalate removal step. 

Keywords

Main Subjects


  1. Ziegler K, Holzkamph E, Breil H, Martin H (1955) Das Mulheimer normaldruck polyathylen verfahren. Angew Chem 67: 541-636
  2. Natta G (1955) Une nouvelle classe de polymers d’ α-olefines ayant une regularite de structure exceptionnelle. J Polym Sci 16: 143-154
  3. Natta G (1956) Stereospezifische katalysen und isotaktische polymere. Angew chem 68: 393-424
  4. Keszler B, Bodor G, Simon A (1980) Studies on highly active coordination catalysts for polymerization of α-olefins:1. X-ray diffractomeric invesigations of the catalyst supports. Polymer 21: 1037-1040
  5. Pino P, Fochi G, Piccolo O, Gianni U (1982) Experimental evidence for the existence of catalytic sites with different steric structures in supported Ziegler-Natta catalysts. J Am Chem Soc 104: 7381-7383
  6. Soga K, Sano T, Yamamoto K, Shiono T (1982) The role additives on the improvement of the isotacticity of polepropylene-A possible interpretation. Chem Lett 12: 425-428
  7. Chien JCW, Wu JC, Kuo CI (1983) Magnesium chloride supported high-mileage catalysts for olefin polymerization. IV. FTIR and quantitative analysis of modifiers in the catalysts. J Polym Sci Polym Chem Ed 21: 725-736
  8. Doi Y, Soga K, Murata M, Suzuki E, Ono Y, Keii T (1983) Additive effect of metal chiorides on propylene polymerization with a soluble titanium-based Ziegler catalyst. Polym commun 24: 244-246
  9. Keszler B, Bodor G, Simon A (1984) Studies on highly active coordination catalysts for polymerization of α-olefins:1. X-ray diffractomeric investigations of the catalyst supports. Polymer 21: 1037-1040
  10. Busico V, Corradini P, Martino LD, Proto A (1986) Polymerization of propene in the presence of MgCl2-supported Ziegler-Natta catalysts, 2a) effects of the co-catalyst composition. Makromol Chem 187: 1115-1124
  11. Terano M, Kataoka T, Keii T (1989) Stopped flow polymerization of propene with typical MgCl2- supported high-yield catalysts. J Mol catal 56: 203-210
  12. Chujo R, Kogure Y, Vaananen T (1994) Two-site model analysis of 13C NMR of polypropylene polymerized by Ziegler-Natta catalyst with external alkoxysilane donors. Polymer 35: 339-342
  13. Harkonen M, Seppala JV, Chujo R, Kogure Y (1995) External silane donors in Ziegler-Natta catalysis: a two-site model simulation of the effects of various alkoxysilane compounds. Polymer 36: 1499-1505
  14. Chujo R, Shimozawa K, Saito M, Kataoka T, Nishiyama I, Ishida M, Sawa N (2000) Internet system for the determination of stochastic parameters in the two-site model in olefin polymerization, Progress and development of catalytic olefin polymerization, Technology and Education Publishers. Tokyo, 264-271
  15. Shimozawa K, Saito M, Kataoka T, Chujo R (2002) Effect of internal donors in propylene polymerization analyzed with the two-site model. Polym Int 51: 530-533
  16. Taniike T, Terano M, (2007) Coadsorption and support-mediated interaction of Ti species with ethyl benzoate in MgCl2-supported heterogeneous Ziegler-Natta catalysts studied by density functional calculations. Makromol Chem Rapid Commun 28: 1918-1922
  17. Correa A, Piemontesi F, Morini G, Cavallo L (2007) Key elements in the structure and function relationship of the MgCl2/TiCl4/lewis base Ziegler−Natta catalytic system. Macromolecules 20: 9181-9189
  18. Taniike T, Funako T, Terano M(2014) Multilateral characterization for industrial Ziegler-Natta catalysts toward elucidation of structure-performance relationship. J Catal 311: 33-40
  19. Ratanasak M, Rungrotmongkol T, Saengsawang O, Hannongbua A (2014) Towards the design of new electron donors for Ziegler-Natta catalyzed propylene polymerization using QSPR modeling. Polymer 56: 340-345
  20. Funako T, Chammingkwan P, Taniike T, Terano M (2015) Addition of a second alcohol in magnesium ethoxide synthesis as a way to vary the pore architecture of Ziegler-Natta catalysts. Polyolefins J 2: 65-71
  21. Hongmanee G, Chammingkwan P, Taniike T, Terano M (2016) Probing into morphology evolution of magnesium ethoxide particles as precursor of Ziegler-Natta catalysts. Polyolefins J 3: 47-57
  22. Piovano A, D’Amore M, Thushara KS, Groppo E, (2018) Spectroscopic evidences for TiCl4/ donor complexes on the surface of MgCl2- supported Ziegler–Natta catalysts. J Phys Chem C 122:5615-5626
  23. Taniike T, Goto K, Terano M (2015) Active site nature of magnesium dichloride-supported titanocene catalysts in olefin polymerization. Polyolefins J 2: 57-63
  24. Terano M, Kataoka T, Keii T (1986) Analysis of MgCl2-supported high-yield catalysts by thermal analysis and infrared spectroscopy. Macromol Chem Rapid Commun 7: 725-731
  25. Terano T, Kataoka T, Keii T (1987) A study on the states of ethyl benzoate and TiCl4 in MgCl2- Supported high-yield catalysts. Makromol Chem 188: 1477-1487
  26. Ohashi R, Saito M, Fujita T, Nakai T, Utsumi H, Deguchi K, Tansho M, Shimizu T (2012) Observation of 47,49Ti NMR Spectra of TiCl4/ MgCl2 catalysts under an ultrahigh magnetic field. Chem Lett 41: 1563-1565
  27. Vittoria A, Meppelder A, Friederichs N, Busico A, Clipullo R (2020) Ziegler–Natta catalysts: Regioselectivity and “hydrogen response”. ACS Catal 10: 644-651
  28. Piovano A, Wada T, Amodio A, Takasao G, Ikeda T, Zhu D, Terano M, Chammingkwan C, Groppo E, Taniike T(2021) Formation of highly active Ziegler–Natta catalysts clarified by a multifaceted characterization approach. ACS Catal 11(22): 13782-13796
  29. Saito M, Murata M, Kataoka T, Sakuda Y, Takahashi H (Received 2021) Characterization of electronic properties of titanium atom in heterogeneous Ziegler-Natta catalyst analyzed by Soft X-ray Emission Spectrometer (SXES). Bulletin of the Chemical Society of Japan 95: 367-373
  30. Piovano A, Groppo E, (2022) Flexible ligands in heterogeneous catalysts for olefin polymerization: Insights from spectroscopy. Coordinat Chem Rev 451: 214258
  31. Abis L, Albizzati E, Giannini U, Giunchi G, Santoro E, Noristi L (1988) Cross polarization/ magic angle spinning 13C solid state nuclear magnetic resonance of model compounds related to supported Ziegler-Natta catalysts. Makromol Chem 189: 1595-1601
  32. Terano M, Saito M, Kataoka T (1992) Solid-state 13C NMR study on the state of the electron donor in MgCl2-supported catalysts. Makromol Chem Rapid Commun 13: 103-108
  33. Ishii K, Mori T, Fujita T (1994) An NMR analysis of coordination of alkoxysilane compounds on MgCl2-supported Ziegler-Natta catalyst. Kobunshi Ronbunshu 51: 685-687
  34. Sormunen P, Hjertberg T, Iiskora E (1990) A solid-state 13C NMR study on heterogeneous Ziegler-Natta vatalyst components. Makromol Chem 191: 2663-2673
  35. Saito M, Uozumi T, Sugano T, Kataoka T, Chujo R (2018) Correlation between catalyst performance and relaxation time of electron donor in olefin polymerization catalyst by solid 13C NMR. Kobunshi Ronbunshu 75(6): 570-575
  36. Bloembergen N, Purcell EM, Pound RV (1948) Relaxation effects in nuclear magnetic resonance absorption. Phys Rev 73: 679-712
  37. Torchia DA (1978) The Measurement of proton-enhanced carbon-13 T1 values by a method which suppresses artifacts. J Magnetic Resonance 30: 613-616
  38. Peng Liang,Wei Li, Yuming Chen, Chuanding Dong,Qi Zhou, Yirong Feng, Mei Chen, Jincheng Dai, Congjing Ren, Binbo Jiang, Jingdai Wang, Yongrong Yang(2021) Revealing the dynamic behaviors of tetrahydrofuran for tailoring the active species of Ziegler–Natta catalysts. ACS Catal 11: 4411-4421
  39. Apperley DC, Harris RK, Hodgkinson P (2012) Solid-state NMR basic principles & practice, Momentum press, New York, Chapter7: Relaxation exchange & quantitation
  40. Rohr KS, Spiess HW (1994) Multidimensional Solid-State NMR and Polymers. Anthropology Culture and Society, 1st ed Academic Press,127
  • Receive Date: 24 December 2021
  • Revise Date: 22 February 2022
  • Accept Date: 12 March 2022
  • First Publish Date: 18 March 2022