Discovery and development of metallocene-based polyolefins with special properties

Document Type : Review

Authors

Institute for Technical and Macromolecular Chemistry, University of Hamburg Bundesstr. 45, 20146 Hamburg, Germany

Abstract

Beside Ziegler-Natta and Phillips catalysts the development of methylaluminoxane (MAO) as cocatalyst in combination with metallocenes or other transition metal complexes for the polymerization of olefins has widely increased the possibilities in controlling the polymer composition, polymer structure, tacticity and special properties with high precision. These catalysts allow the synthesis of isotactic, isoblock, syndiotactic, stereoblockor atactic polymers, as well as polyolefin composite materials with superior properties such as film clarity, tensile strength and lower content of extractables. Metallocene and other single site catalysts are able to copolymerize ethene and propene with short and long chained a-olefins, cyclic olefins, or polar vinyl monomers such as ethers, alcohols or esters, especially, if the polar monomers are protected by aluminum alkyls. Different vinyl ethers such as vinyl-ethyl ether, vinyl-propyl ether, vinyl-hexyl ether, and 2,7-octadienyl methyl ether (MODE) were copolymerized with olefins using triisobutyl aluminum as protecting agents. Polar monomers could be incorporated into the polymer chain by up to 16 mol%. Such copolymers show better gas barrier and surface properties, as well as solvent resistance and they are suitable for blends of polyolefins with polyethers and other polar polymers because of an excellent adhesion of the two polymers.

Keywords

Main Subjects


  1. Kaminsky W (2008) Trends in polyolefin chemistry. Macromol Chem Phys 209: 459-466
  2. Kaminsky W, Vollmer H-J, Heins E, Sinn H (1970) The formation of dimetalloalkylene, a unavoidable Side Reaction in homogeneous Ziegler-Catalysts Makromol Chem 175: 443-456
  3. Mottweiler R (1975) Investigation of the reaction of biscylopentadienyl titanium compounds and aluminum alkyls, in the presents of ethylene. Thesis, University of Hamburg
  4. Andresen A, Cordes H-G, Herwig J, Kaminsky W, Merck A, Mottweiler R, Pein J, Sinn H, Vollmer H-J, (1976) Halogen-free soluble Ziegler catalysts for the polymerization of ethylene. Control of molecular weight by choice of temperature. Angew Chem Int Ed Engl 15: 630-631
  5. Kaminsky W (2004) The discovery of metallocene catalysts and their present state of the art. J Polym Sci Part A: Polym Chem 42: 3911-3921
  6. Kaminsky W (2012) Discovery of methylaluminoxane as cocatalyst for olefin polymerization. Macromolecules 45: 3289-3297
  7. Bliemeister J, Hagendorf W, Harder A, Heitmann B, Schimmel I, Schmedt E, Schnuchel W, Sinn H, Tikwe L, vThienen N, Urlass K, Winter H, Zarncke O (1995) The role of MAO activators. In: Ziegler catalysts, Fink G, Mülhaupt P, Brintzinger HH (eds), Springer, Berlin, 57-82
  8. Eilertsen JL, Rytter E, Ystenes (1999) In situ FTIR spectroscopy shows no evidence of reaction between MAO and TMA. In: metalorganic catalysts for synthesis and polymerization, Kaminsky W (ed), Springer, Berlin, 136-141
  9. Yang X, Stern CL, Marks TJ (1991) Models for organometallic molecule-support complexes. Very large counterion modulation of cationic actinide alkyl reactivity. Organometallics 10: 840-842
  10. Bochmann M (2010) The chemistry of catalyst activation: The case of group 4 polymerization catalysts. Organometallics 29: 4711-4740
  11. Scheirs J, Kaminsky W (eds.) (2000) Metallocene based polyolefins: Preparation, properties, and technology, Wiley, Chichester, UK, Vols. 1 and 2
  12. Zhang J, Wang X, Jin G-X (2006) Polymerized metallocene catalysts and late transition metal catalysts for ethylene polymerization. Coordination Chem Rev 250: 95-109
  13. Coates GW (2000) Precise control of polyolefin stereochemistry using single-site metal catalysts. Chem Rev 100: 1223-1252
  14. Rieger B, Baugh LS, Kacker S, Striegler S (eds) (2003) Late transition metal polymerization catalysis, Wiley-VCH, Weinheim
  15. Razavi A, Thewalt U (2006) Site selective ligand modification and tactic variation in polypropylene chains produced with metallocene catalysts. Coordination Chem Rev 250: 155-169
  16. Kaminsky W (ed.) (2005) Olefin polymerization. Macromol Symp 236
  17. Kaminsky W, Luinstra GA (2010) Olefin polymerization by metallocene catalysis. Edition Ostwald: On Catalysis. Reschetilowski W, Hönle (eds) VWB-press, Berlin Vol 2, 186-214
  18. Nomura K, Liu KJ (2011) Half-titanocenes for precise olefin polymerization: Effect of ligand substituents and some mechanistic aspects. Dalton Trans 40: 7666-7682
  19. Kaminsky W (Ed) (2013) Polyolefins: 50 years after Ziegler and Natta. Vol I and II, Advances in Polymer Science 257 and 258, Springer, Heidelberg
  20. Delferro M, Marks TJ (2011) Multinuclear olefin polymerization catalysts. Chem Rev 111: 2450-2485
  21. Brintzinger HH, Fischer D, Mülhaupt R, Waymouth RM (1995) Stereospecific olefin polymerization with chiral metallocene catalysts. Angew Chem Int Ed Engl 34:1143-1170
  22. Alt GH, Milius W, Palackal SJ (1994) Bridged bis(fluorenyl) complexes of zirconium and hafnium as highly reactive catalysts in homogeneous olefin polymerization. J Organomet Chem 472: 113-118
  23. Kaminsky W, Engehausen R, Zoumis K, Spaleck W, Rohrmann J (1992) Standardized polymerization of ethylene and propene with bridged and unbridged metallocene derivates: A comparism. Makromol Chem 193: 1643-1651
  24. Kaminsky W (1996) New polymers by metallocene catalysis. Macromol Chem Phys 197: 3907-3945
  25. Okuda J, Schattenmann FJ, Wocadlo S, Massa W (1995) Synthesis and characterization of zirconium complexes containing a linked amido fluorenyl ligand. Organometallics 14: 789-795
  26. Kawai K, Fujita T (2009) Metal catalysts in olefin polymerization. Top Organomet Chem 26: 3-46
  27. Damavandi S, Zohuri GH, Ahmadjo S, Sandaroos R, Shamekhi MA (2014) Synthesis of high molecular weight polyethylene using FI catalysts. Polyolefins J 1: 25-32
  28. Hlatky GG (2000) Heterogeneous single-site catalysts for olefin polymerization. Chem Rev 100: 1347-1376
  29. Wild FR, Zsolnai L, Huttner G, Brintzinger HH (1982) ansa-metallocene derivates. IV. Synthesis and molecular structure of chiral ansa-titanocene derivates with bridged tetrahydroindenyl ligands. J Organomet Chem 232: 233-247
  30. Kaminsky W, Külper K, Brintzinger HH, Wild FR (1985) Polymerization of propene and butane with a chiral zirconocene and methylalumoxane as cocatalyst. Angew Chem Int Ed Engl 24: 507- 508
  31. Ewen JA, Jones RL, Razavi A, Ferrara JP (1988) Syndiospecific propylene polymerization with group IVB metallocenes. J Am Chem Soc 110: 6255-6256
  32. Razavi A (2013) Syndiotactic polypropylene: Discovery, development, and industrialization via bridged metallocene catalysts. Adv Polym Sci 258: 43-116
  33. Resconi l, Cavallo L, Fait A, Piemontesi F (2000) Selectivity in propene polymerization with metallocene catalysts. Chem Rev 100: 1253-1345
  34. McNally T, Poetschke P Eds. (2011) Polymercarbon nanotube composites: Preparation, properties, and applications. Woodhead Publishing, Cambridge, UK
  35. Alexandre M, Martin E, Dubois P, Marti MG, Jerome R (2001) Polymerization filling technique: an efficient way to improve the mechanical properties of polyethylene composites. Chem Mater 13: 236-237
  36. Kaminsky W (2014) Metallocene based polyolefin nanocomposites. Materials 7: 5069-5108
  37. Kaminsky W, Funck A, Klinke C (2008) In-situ polymerization of olefins on nanoparticles or fibers by metallocene catalysts. Top Catal 48: 84-90
  38. Funck A, Kaminsky W (2007) Polypropylene carbon nanotube composites by in-situ polymerization with metallocene/MAO catalysts.Composites Sci and Technol 67: 906-915
  39. Lozano K, Bonilla-Rios J, Barrera EV (2001) Nanofiber reinforced thermoplastic composites: Thermoanalytic and mechanical analysis. J Appl Polym Sci 80: 1162-1172
  40. Stadler FJ, Arikan-Conley B, Kaschta J, Kaminsky W, Münstedt H (2011) Synthesis and characterization of novel ethylene-graft-ethylene/ propylene copolymers. Macromolecules 44: 5053-5063
  41. Kaminsky W, Boggioni L, Tritto I (2012) Cycloolefin polymerization. Polym Sci A comp Ref 3: 843-873
  42. Frediani M, Bianchini C, Kaminsky W (2006) Low density polyethylene by tandem catalysis with single site Ti(IV)/Co(II) catalysts. Kinet Catal 47: 207-212
  43. Arikan B, Stadler FJ, Kaschta J, Münstedt H, Kaminsky W (2007) Synthesis and characterization of novel ethene-graft ethene/ propene copolymers. Macromol Rapid Commun 28: 1472-1478
  44. Kaminsky W, Spiehl R (1989) Copolymerization of cycloalkenes with ethylene in presence of chiral zirconocene catalysts. Makromol Chem 190: 515-526
  45. Boggioni L, Tritto I (2014) Propene- cycloolefin polymerization. Polyolefins J 1:61-75
  46. Kaminsky W, Tran PD, Werner R (2004) New polymers by copolymerization of ethylene and norbornene with metallocene catalysts. Macromol Symp 213: 101-108
  47. Seppälä J, Kokko E, Lehmus P, Malmberg AP, Hakala K, Lipponen S, Löfgren B (2013) Funktional polyolefins through polymerization by using bis(indenyl)zirkonium catalysts. Adv Polym Sci 2013: 179-232
  48. Kesti MR, Coates GW, Waymouth RM, (1992) Homogeneous Ziegler-Natta polymerization of functionalized monomers catalyzed by cationic Group IV metallocenes. J Am Chem Soc 114: 9679-9680
  49. Kaminsky W, Fernandez M (2008) New polymers by copolymerization of olefins with bio oil components. Eur J Lipid Sci Technol 110: 841- 845
  50. Busico V, Cipullo R, Corradini P (1993) Macromol Chem Rapid Commun 117: 195.
  51. Stadler FJ, Arikan B, Kaschta J, Kaminsky W (2010) Long-chain branches in syndiotactic polypropene induced by vinyl chloride. Macromol Chem Phys 211: 1472-1481
  52. Kaminsky W, Funck A, Hähnsen H (2009) New application for metallocene catalysts in olefin polymerization. J Chem Soc Dalton Trans 2009: 8803-8810
  53. Imuta J, Kashiwa N, Toda Y (2002) Catalytic regioselective introduction of allyl alcohol into the nonpolar polyolefins: Development of one pot synthesis of hydroxyl-capped polyolefins mediated by a new FI catalyst. J Am Chem Soc 124: 1176-1177
  54. Lipponen S, Seppälä J (2011) Ethylenebis(indenyl)zirconium dichlo-ride/Methylaluminoxane catalyzed copolymerization of ethylene and 1- alkenen-trimethylsilanes. Organometallics 30: 528-533
  55. Busico V (2009) Metal-catalysed olefin polymerisation into the new millenium: A perspective outlook. Dalton Trans 41: 8794-8802