Skip to main content
Log in

Ethene/norbornene copolymerization by [Me2Si(3-tertBuCp)(NtertBu)]TiCl2/MAO-catalyst

  • Chemistry & Biochemical Engineering
  • Published:
Journal of Zhejiang University-SCIENCE A Aims and scope Submit manuscript

Abstract

Ethene/norbornene copolymerization by the catalyst system [Me2Si(3-tertBuCp)(NtertBu)]TiCl2/MAO was investigated in detail at 30 °C, 60 °C, and 90 °C. A mass flow controller was used in this work to obtain kinetic data and investigate temperature's effects on activity, norbornene incorporation, copolymerization parameter, microstructure, glass transition temperature, and molar masses were described. High copolymerization valuesr ξ and high alternation are determined. The number of isotactic alternating sequences is much higher than that of the syndiotactic alternating sequences.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Similar content being viewed by others

References

  • Altamura, P. and Grassi, A., 2001. Crystalline Alternating Sequences identified in ethylene-co-norbornene polymers produced by the (η5-C2B9H11) Zr (NEt2)2 (NHEt2)-AliBu3 catalyst.Macromolecules,34:9197–9200.

    Article  Google Scholar 

  • Arndt, M. and Beulich, I., 1998. C1-symmetric metallocenes for olefin polymerisation, 1: Catalytic performance of [Me2C(3-tertBuCp)(Flu)]ZrCl2 in ethene/norbornene copolymerisation.Macromol. Chem. Phys.,199: 1221–1232.

    Google Scholar 

  • Arndt-Rosenau, M. and Beulich, I., 1999. Microstructure of Ethene/Norbornene Copolymers.Macromolecules,32 (22): 7335–7343.

    Article  Google Scholar 

  • Bergström, C. H. and Seppälä, J. V., 1997. Effects of polymerization conditions when making norbornene-ethylene copolymers using the metallocene catalyst ethylene bis (indenyl) zirconium dichloride and MAO to obtain high glass transition temperatures.J. Appl. Polym. Sci.,63: 1063–1070.

    Article  Google Scholar 

  • Beulich, I., 1999. Copolymerisation von Ethen und sterisch anspruchsvollen Olefinen durch Metallocen-Katalysatoren. Dissertation, University Hamburg, Germany.

    Google Scholar 

  • Brekner, M. J., Osan, F., Rohrmann, J. and Antberg, M., 1992. Process for the preparation of chemically homogeneous cycloolefin copolymers. Patent US 5 324 801.

  • Canich, J. A. M., 1997. Monocyclopentadienyl metal compounds for ethylene-alpha-olefin-copolymer production catalysts. Patent US 5 631 126.

  • Cherdron, H., Brekner, M. J. and Osan, F., 1994. Cycloolefin-Copolymere: Eine neue Klasse transparenter Thermoplaste.Angew. Makromol. Chem.,223: 121–133.

    Article  Google Scholar 

  • Ewen, J. A., Elder, M. J., Jones, R. L., Haspeslagh, L., Atwood, J. L., Bott, S. G. and Robinson, K., 1991. Metallocene/polypropylene structural relationships: implications on polymerization and stereochemical control mechanisms.Makromol. Chem. Macromol. Symp.,48/49: 253–295.

    Article  Google Scholar 

  • Forsyth, J., Pereña, J. M., Benavente, R., Pérez, E., Tritto, I., Boggioni, L. and Brintzinger, H. H., 2001. Influence of the polymer microstructure on the thermal properties of cycloolefin copolymers with high norbornene contents.Macromol. Chem. Phys.,202 (5):614–620.

    Article  Google Scholar 

  • Goodall, B. L. and Lester, H. McI, 2001. Method for the preparation of copolymers of ethene/norbornene-type monomers with cationic palladium catalysts. Patent US 6 265 506.

  • Harrington, B. A. and Crowther, D. J., 1998. Stereoregular, alternating ethylene-norbornene copolymers from monocyclopentadienyl catalysts activated with non-coordinating discrete anions.J. Mol. Catal. A: Chem.,128: 79–84.

    Article  Google Scholar 

  • Jansen, J. C., Mendichi, R., Locatelli, P. and Tritto, I., 2001. Evidence of the quasi-living character of the ansa-Zirconocene/MAO-catalyzed copolymerization of ethylene and norbornene.Macromol. Rapid Commun.,22: 1394–1398.

    Article  Google Scholar 

  • Kaminsky, W. and Spiehl, R., 1989. Copolymerization of cycloalkenes with ethylene in presence of chiral zirconocene catalyst.Makromol. Chem.,19:515.

    Article  Google Scholar 

  • Kaminsky, W., Arndt, M. and Bark, A., 1991. New results of the polymerization of olefins with metallocene/aluminoxane-catalysts.Polym. Prep.,1:467.

    Google Scholar 

  • Kaminsky, W. and Noll, A., 1993. Copolymerization of Norbornene and Ethene with Homogeneous Zirconocenes/Methylaluminoxane Catalysts.Polymer Bulletin,31:175.

    Article  Google Scholar 

  • Kiesewetter, J. and Kaminsky, W., 2002. Ethene/Norbornene copolymerization with Palladium (II) α-Diimine catalysts from ligand screening to discrete catalysts species.Chem. Eur. J., accepted.

  • Lamonte, R. R. and McNally, D., 2001. Cyclic olefin copolymers.Advanced Materials & Process.

  • Landolt-Börnstein, 1976. Zahlenwerte und Funktionen aus Physik Chemie Astronomie Geophysik Technik, Springer, Berlin, 6th edition, Part 4, C2: p. 121.

    MATH  Google Scholar 

  • Laserov, H., Mönkkönen and Pakkanen, T. T., 1998. Influence of batch reaction conditions on norbornene/ethylene copolymers made using C2v- and Cs-symmetric metallocene/MAO.Macromol. Chem. Phys.,199: 1939–1942.

    Article  Google Scholar 

  • McKnight, A. L. and Waymouth, R. M., 1999. Ethylene/ Norbornene Copolymerizations with Titanium CpA Catalysts.Macromolecules,32:2816–2825.

    Article  Google Scholar 

  • Rische, T., Waddon, A. J., Dickinson, L. C. and MacKnight, W. J., 1998. Microstructure and Morphology of Cycloolefin Copolymers.Macromolecules,31: 1871–1874.

    Article  Google Scholar 

  • Ruchatz, D. and Fink, G., 1998. Ethene-Norbornene Copolymerization Using Homogeneous Metallocene and Half-Sandwich Catalysts: Kinetics & Relationship between Catalyst Structure & Polymer Structure.Macromolecules,31:4669–4686.

    Article  Google Scholar 

  • Thorshaug, K., Mendichi, R., Boggioni, L., Tritto, I., Trinkle, S., Friedrich, C. and Mülhaupt, R., 2002. Poly(ethene-co-norbornene) obtained with a constrained geometry catalyst. A study of reaction kinetic and copolymer properties.Macromolecules,35 (8): 2903–2911.

    Article  Google Scholar 

  • Tran, Ph-Dennis, 1999. Ethen/Norbornen-Copolymerisation durch Metallocenkatalysatoren. Diploma thesis, University Hamburg, Germany.

    Google Scholar 

  • Tritto, I., Marestin, C., Boggioni, L., Zetta, L., Provasoli, A. and Ferro, D. R., 2000. Ethylene-norbornene copolymer microstructure. Assessment and advances based on assignments of 13C NMR Spectra.Macromolecules,33: 8931–8944.

    Article  Google Scholar 

  • Tritto, I., Marestin, C., Boggioni, L., Sacchi, M. C., Brintzinger, H. H. and Ferro, D. R., 2001. Stereoregular and Stereoirregular Alternating Ethylene-Norbornene Copolymers.Macromolecules,34 (17): 5770–5777.

    Article  Google Scholar 

  • Yoshida, Y., Saito, J., Mitani, M., Takagi, Y., Matsui, S., Ishii, S., Nakano, T., Kashiwa, N. and Fujita, T., 2002. Living ethylene/norbornene copolymerization catalyzed by tatanium complexes having two pyrrolideimine chelate ligands.Chem. Commun.,0 (12): 1298–1299.

    Article  Google Scholar 

  • Wang, Q., Weng, J., Fan, Z. and Feng, L., 1997. Influence of mixed aluminoxane system on ethylene-norbornene copolymerization catalyzed by metallocene.Macromol. Rapid Commun.,18: 1101–1107.

    Article  Google Scholar 

  • Wendt, R. A., Mynott, R., Hauschild, K., Ruchatz, D. and Fink, G., 1999. 13C NMR studies of ethene-norbornene copolymers: assigment of sequence distributions using 13C— enriched monomers and determination of the copolymerization parameters.Macromol. Chem. Phys.,200: 1340–1350.

    Article  Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Kaminsky Walter.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Tran, PD., Kaminsky, W. Ethene/norbornene copolymerization by [Me2Si(3-tertBuCp)(NtertBu)]TiCl2/MAO-catalyst. J. Zhejiang Univ. Sci. A 4, 121–130 (2003). https://doi.org/10.1631/jzus.2003.0121

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1631/jzus.2003.0121

Key words

Document code

CLC number

Navigation