Propene-cycloolefin polymerization

Document Type: Review


Instituto per lo Studio delle Macromolecole, Consiglio Nazionale delle Ricerche Via E. Bassini 15, 20133 Milano, Italy


Highly active metallocenes and other single site catalysts have opened up the possibility of polymerizing cycloolefins such as norbornene (N) or of copolymerizing them with ethene (E) or propene (P). The polymers obtained show exciting structures and properties. E-N copolymers are industrially produced materials, with variable and high glass transitions depending on the wide range of their microstructures. By realizing the possibility in great variety of stereoregularity of propene and norbornene units and the difference in comonomer distribution, P-N copolymers were expected to have fine tuned microstructures and properties. Moreover, P-N copolymers should be characterized by higher Tg-values than E-N copolymers with the same norbornene content and molar mass. A review of the state of the art of P-N copolymerization by ansa-metallocenes of C2 symmetry, namely rac-Et(Ind)2ZrCl2 (I-I) and rac-Me2Si(Ind)2ZrCl2 (I-II), and rac-Me2Si(2-Me-Ind)2ZrCl2 (I-III), and of catalysts of Cssymmetry, namely (tBuNSiMe2Flu)TiMe2 (IV-I) and derivatives, is given here. Special emphasis is given to microstructural studies of P-N copolymers, including stereo- and regioregularity of propene units as well as of comonomer distribution, stereoregularity of norbornene units, and the structure of chain end-groups. This information allows us to find a rationale for the catalytic activities and the copolymer properties.


Main Subjects

  1. Brintzinger HH, Fischer D, Mülhaupt R, Rieger B, Waymouth R (1995) Stereospecific olefin polymerization with chiral metallocene catalysts. Angew Chem Int Ed Engl 34:1143-1170
  2. Resconi L, Cavallo L, Fait A, Piemontesi F (2000) Selectivity in propene polymerization with metallocene catalysts. Chem Rev 100:1253-1345
  3. Ewen JA, Jones RL, Razavi A, Ferrara JD (1988) Syndiospecific propylene polymerizations with group 4 metallocenes. J Am Chem Soc 110:6255- 6256
  4. Spaleck W, Antberg M., Dolle V, Klein R, Rohrmann J, Winter A, (1990) Stereorigid metallocenes:correlation between structure and behavior in homopolymerizations of propylene. New J Chem 14:499-503
  5. Ewen JA, Elder MJ, Jones RL, Haspeslagh L, Atwood J, Bott SG, Robinson K (1991) Metallocene polypropylene structural relationships - implications on polymerization and stereochemical control mechanisms. Makromol Chem, Rapid Commun 48/49:253-259
  6. Razavi A, Atwood JL (1995) Preparation and crystal-structures of the complexes (η5-C5H3Me- CMe25-C13H8)MCl2 (M=Zr or Hf) - mechanistic aspects of the catalytic formation of a syndiotactic-isotactic stereoblock-type polypropylene. J Organomet Chem 497:105-111
  7. Farina M, Terragni A (1993) n the syndiotactic polymerization mechanism using metallocene catalysts. Makromol Chem Rapid Commun 14:791-798
  8. Razavi A, Peters L, Nafpliotis L, Vereecke D, Den Dauw K (1995) The geometry of the site and its relevance for chain migration and stereospecificity. Macromol Symp 89:345-367
  9. Busico V, Cipullo R, Talarico G, Segre AL, Caporaso L (1998) High-field 13C NMR characterization of ethene-1-C-13/propene copolymers prepared with C-s-symmetric ansa-metallocene catalysts:A deeper insight into the regio- and stereoselectivity of syndiotactic propene polymerization. Macromolecules 31:8720-8724
  10. Sartori G, Ciampelli FC, Cameli N (1963) Polymerization of norborene Chim Ind 45:1478- 1482
  11. Kaminsky W, Bark A, Arndt M (1991) New polymers by homogenous zirconocene aluminoxane catalysts. Makromol Chem Macromol Symp 47:83-93
  12. Kaminsky W, Arndt-Rosenau M, Scheirs J (2000) Metallocene-based Polyolefins, Wiley, Chichester, 91
  13. Blank F, Janiak C (2009) Metal catalysts for the vinyl/addition polymerization of norbornene. Coord Chem Rev 253:827-861
  14. Tritto I, Boggioni L, Ferro DR (2006) Metallocene catalyzed ethene- and propene co-norbornene polymerization:Mechanisms from a detailed microstructural analysis. Coord Chem Rev 250:212-241
  15. Kaminsky W, Boggioni L, Tritto I (2012) Cycloolefin Polymerization. In:Matyjaszewski K, Möller M (Eds) Polymer Science:A Comprehensive Reference. Elsevier, Amsterdam, 843
  16. Provasoli A, Ferro DR, Tritto I, Boggioni L (1999) The conformational characteristics of ethylene-norbornene copolymers and their influence on the 13C NMR spectra. Macromolecules 32:6697-6706
  17. Tritto I, Boggioni L, Sacchi MC, Locatelli P, Ferro DR, Provasoli A ( 1999) Ethylene-norbornene copolymers prepared with metallocene-based catalysts:new sequence assignments by C-13 NMR. Macromol Rapid Commun 20:279-283
  18. Arndt M, Beulich I (1998) C1-symmetric metallocenes for olefin polymerisation, 1-catalytic performance of [Me2C(3-(BuCp)-tBu)(Flu)] ZrCl2 in ethene/norbornene copolymerisation. Macromol Chem Phys 199:1221-1232
  19. Ruchatz D, Fink G (1998) Ethene-norbornene copolymerization using homogenous metallocene and half-sandwich catalysts: Kinetics andrelationships between catalyst structure and polymer structure. 2. Comparative study of different metallocene- and half-sandwich methylaluminoxane catalysts and analysis of the copolymers by C-13 nuclear magnetic resonance spectroscopy. Macromolecules 31:4674-4680
  20. http// and Brekner M. J, Osan F, Rohrmann J, Antberg M (1994) Process for the preparation of chemically homogeneous cycloolefin copolymers, U.S. Patent 5 324 801, pp:199
  21. Henschke O, Köller F, Arnold M (1997) Polyolefins with high glass transition temperatures. Makromol Rapid Commun 18:617
  22. Boggioni L, Bertini F, Zannoni G, Tritto I, Carbone P, Ragazzi M, Ferro DR (2003) Propene-norbornene copolymers:Synthesis and analysis of polymer structure by 13C NMR spectroscopy and ab initio chemical shift computations. Macromolecules 346:882-890
  23. Boggioni L, Tritto I, Ragazzi M, Carbone P, Ferro DR (2004) Propene-norbornene copolymers: synthesis and microstructure. Macromol Symp 218:39-50
  24. Carbone P, Ragazzi M, Tritto I, Boggioni L, Ferro DR (2003) Ab initio molecular modeling of 13C NMR chemical shifts of polymers. 2. Propene-norbornene copolymers. Macromolecules 36:891-899
  25. Kaminsky W, Derlin S, Hoff M (2007) Copolymerization of propylene and norbornene with different metallocene catalysts. Polymer 48:7271-7278
  26. Hasan T, Ikeda T, Shiono T (2005) Random copolymerization of propene and norbornene with ansa-fluorenylamidodimethyltitanium-based catalysts. Macromolecules 38:1071-1074
  27. Boggioni L, Zampa C, Ravasio A, Ferro DR, Tritto I (2008) Propene-norbornene copolymers by C2-symmetric metallocene rac- Et(Ind)2ZrCl2:influence of reaction conditions on reactivity and copolymer properties. macromolecules 41:5107-5115
  28. Boggioni L, Ravasio A, Zampa C, Ferro DR, Tritto I (2010) Penultimate Effects and Chain Epimerization in Propene-Norbornene Copolymers by rac-Me2Si(2-Me-Ind)2ZrCl2 C2-Symmetric Metallocene. Macromolecules 43:4532-4542
  29. Boggioni L, Ravasio A, Boccia AC, Ferro DR, Tritto I (2010) Propene-norbornene copolymers toward a description of microstructure at triad level based on assignments of C-13 NMR spectra. Macromolecules 43:4543-4556
  30. Dougnac VN, Peoples BC, Rebagliati FM, Galland GB, Quijada R (2012) Study on the copolymerization of propylene with norbornene using metallocene catalysts. Polym Bull 69:925- 935
  31. Hasan T, Nishii K, Shiono T, Ikeda T (2002) Living polymerization of norbornene via vinyl addition with ansa-fluorenylamidodimethyl titanium complex. Macromolecules 35:8933- 8935
  32. Cai Z, Harada R, Nakayama Y, Shiono T (2010) Synthesis of Stereoblock polypropylene by change of temperature in living polymerization. Macromolecules 43:4527-4531
  33. Carvill A, Zetta L, Zannoni G, Sacchi MC (1998) ansa-zirconocene-catalyzed solution polymerization of propene:influence of polymerization conditions on the unsaturated chain-end groups. Macromolecules 31:3783-3789
  34. Shiono T (2011) Living polymerization of olefins with ansa-dimethyl-silylene(fluorenyl)(amido) dimethyltitanium-based catalysts. Polym J 43:331-351
  35. Lin WF, Hsiao TJ, Tsai JC, Chung TM, Ho RM (2008) Syntheses of polyolefin-based stereoregular diblock copolymers for self-assembled nanostructures. J Polym Sci, Part A:Polym Chem 46:4843-4856
  36. Lin WF, Tsai JC (2008) The comonomer inducing selective beta-methyl elimination chain transfer:a new approach for end-functionalizations of syndiotactic polypropylene-based copolymers. J Polym Sci, Part A:Polym Chem 46:2167-2176