Effect of the synthesis conditions of titanium-magnesium catalysts on the composition, structure and performance in propylene polymerization

Document Type : Original research

Authors

Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, Prospect Akademika Lavrentieva 5, Novosibirsk 630090 , Russian Federation

Abstract

Supported catalysts synthesized via the interaction of Mg(OEt)2 with TiCl4 in the presence or absence of an internal stereoregulating donor (di-n-butyl phthalate), with different solvents (chlorobenzene, n-undecane, n-heptane) at different titanation temperatures have been studied by a set of physicochemical methods. Data on the chemical composition, X-ray structure and pore structure of these catalysts as well as data on their activity and stereospecificity in polymerization of propylene were obtained. Chemical composition, structure, activity and stereospecificity depend primarily on the presence of an electron donor stereoregulating component and on the solvent nature and titanation temperature. Activity of the catalysts is determined by totality of different characteristics: the chemical composition, in particular, the presence of inactive by-products like TiCl3(OEt), the MgCl2 X-ray structure and pore structure. More active catalyst which was synthesized under optimal conditions in the presence of di-n-butyl phthalate contains the minimal amount of TiCl3(OEt) by-product, and has a more ordered X-ray structure and a homogeneous mesoporous structure with a narrow mesopore size distribution.

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References

  1. Shijng X, Honglan L, Inghui Z (1990) Studies on TiCl4/Mg(OEt)2/EB supported catalysts catalyst for propylene polymerization. Chinese J Polym Sci 8: 253-260
  2. Jeong Y-T, Lee D-H (1990) Propene polymeriza­tion with Mg(OEt)2 supported TiCl4 catalyst,1. Catalyst composition and behavior. Macromol Chem 191: 1487-1496
  3. Jeong Y-T, Lee D-H, Soga K (1991) Propene po­lymerization with Mg(OEt)2-supported TiCl4 cat­alyst, 2a). Effects of TiCl4 treatment. Macromol Chem, Rapid Commun 12: 5-7
  4. Jeong Y-T, Lee D-H, Shiono T, Soga K (1991) Propene polymerization with Mg(OEt)2-support­ed TiCl4 catalyst. 3a) The role of benzoyl chlo­ride. Macromol Chem 192: 1727-1731
  5. Lee D-H, Jeong Y-T, Soga K, Shiono T (1993) Propene polymerization with Mg(OEt)2/benzoyl chloride/TiCl4-triethylaluminum/external donor catalyst systems. J Appl Polym Sci 47: 1449-1461
  6. Lee D-H, Jeong Y-T (1993) Propene polymeriza­tion with Mg(OEt)2-supported TiCl4 catalyst. – 4. Effect of hydrogen. Eur Polym J 29: 883-888
  7. Chadwick JC, Miedema A, Ruish BJ, Sudmeijer O (1992) Effects of procatalyst composition on the stereospecificity of a Ziegler-Natta catalyst system. Makromol Chem 193: 1463-1468
  8. Kim I, Choi HK, Han TK, Woo SI (1992) Polym­erization of propylene catalyzed over highly ac­tive and stereospecific catalysts synthesized with Mg(OEt)2/Benzoyl Chloride/TiCl4. J Polym Sci, Part A: Polym Chem 30: 2263-2271
  9. Lee D-H, Jeong Y-T, Kang KK (1994) Change of internal donor for Mg(OEt)2–supported TiCl4 cat­alysts. Catalyst design for tailor-made polyolefins 89: 153-163
  10. Kang KK, Shiono T, Jeong Y-T, Lee D-H (1999) Polymerization of propylene by using Mg(OEt)2 –DNBP-TiCl4 Catalyst with disilanes as external Donor. J Appl Polym Sci 71: 293-301
  11. Kang KK, Kim K, Lee D-H, Jeong Y-T (2001) Propene polymerization by using TiCl4 catalyst supported on solvent activated Mg(OEt)2. J Appl Polym Sci 81: 460-467
  12. Tanase S, Katayama K, Inasawa S, Okada F, Yamaguchi Y, Sadashima T, Yabunouchi N, Kon­akazawa T, Junke T, Ishihara N (2008) New synthesis method using magnesium alkoxides as carrier materials for Ziegler-Natta catalysts with spherical morphology. Macromol React Eng 2: 233-239
  13. Tanase S, Katayama K, Inasawa S, Okada F, Ya­maguchi Y, Konakazawa T, Junke T, Ishihara N (2008) Particle growth of magnesium alkoxide as carrier material for polypropylene polymerization catalyst. Appl Catal A-Gen 350: 197-206
  14. Dashti A, Ramazani SA, Hiraoko Y, Kim SY, Tan­like T, Terano M (2009) Kinetic and morphologi­cal study of a magnesium ethoxide-based Ziegler- Natta catalyst for polypropylene polymerization. Polym Int. 58: 40-45
  15. 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
  16. Funako T, Chammingkwan P, Taniike T, Terano M (2015) Alternation of pore architecture of Ziegler-Natta catalysts through modification of magnesium ethoxide. Macromol React Eng 9: 325-332
  17. Makwana UC, Singala KJ, Patankar RB, Singh SC, Gupta VK (2012) Propylene polymerization using supported Ziegler-Natta catalysts systems with mixed donors. J Appl Polym Sci 125: 896- 901
  18. 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
  19. Cherepanova SV, Tsybulya SV (2000) Simulation of X-ray powder diffraction patterns for low-or­dered materials. J Mol Catal A-Chem 158: 263- 266
  20. Cherepanova SV, Tsybulya SV (2004) Simulation of X-ray powder diffraction patterns for one-di­mensionally disordered crystals. Mater Sci Fo­rum 443-4: 87-90
  21. Arzoumanidis GG, Karayannis NM (1991) In­frared spectral characterization of supported pro­pene polymerization catalysts. A link to catalyst performance. Appl Catal 76: 221-231
  22. Utko J, Sobota P, Lis T (1987) The crystal struc­ture of tetrachloro(diethylphthalate)titanium (IV). J Organomet Chem 334: 341-345
  23. Ilyina EV, Mishakov IV, Vedyagin AA, Cherepa­nova SV, Nadeev AN, Bedilo AF, Klabunde KJ (2012) Synthesis and characterization of meso­porous VOx/MgO aerogels with high surface area. Micropor Mesopor Mater 160: 32-40
  24. Garoff T, Iiskola E, Sormunen P (1988) The in­fluence of crystal water on the performance of Ziegler-Natta catalyst in propylene polymeriza­tion. In: Kaminsky WH, Sinn H (Eds.), Transition metals and organometallics as catalysts for olefin polymerization. Springer-Verlag, Berlin-Heidel­berg, 197-208 
Polyolefins Journal
Volume 4, Issue 1 - Serial Number 7
January 2017
Pages 111-122

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History

  • Receive Date: 20 July 2016
  • Revise Date: 03 October 2016
  • Accept Date: 09 October 2016

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