Skip to main content
SpringerLink
Log in

Styrene copolymerization using a metallocenic initiator. Homo- and copolymerization of styrene with isoprene through zirconocene–MAO initiating systems

  • Original Paper
  • Published:
Polymer Bulletin Aims and scope Submit manuscript

Abstract

The copolymerization of styrene with isoprene (Ip) has been tested using combined zirconocene–methylaluminoxane (MAO) initiating system. Both “half-sandwich” and real zirconium-based metallocenes were used. Regardless of the metallocene employed, conversion to copolymer was much influenced by the proportion of Ip in the initial feed. As the proportion of Ip is enriched, conversion to copolymer decreases substantially. Results of NMR and DSC analyses indicate that the products obtained were truly copolymers and not a mixture of both homopolymers. The studied zirconocene–MAO initiating system produces atactic polystyrene. A small amount of Ip in the initial feed substantially diminishes the conversion and at best traces of poly(isoprene) were detected in the homopolymerization of Ip with these initiating systems.

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

Access this article

Log in via an institution

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

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2

Similar content being viewed by others

References

  1. Ishihara N, Seimiya T, Kuramoto M, Uoi M (1986) Crystalline syndiotactic polystyrene. Macromolecules 19:2464–2465

    Article  CAS  Google Scholar 

  2. Ishihara N, Kuramoto M, Uoi M (1988) Stereospecific polymerization of styrene giving the syndiotactic polymer. Macromolecules 21:3356–3360

    Article  CAS  Google Scholar 

  3. Pellecchia C, Longo P, Grassi A, Ammendola P, Zambelli A (1987) Synthesis of highly syndiotactic polystyrene with organometallic catalysts and monomer insertion. Makromol Chem Rapid Commun 8:277–279

    Article  CAS  Google Scholar 

  4. Po R, Cardi N (1996) Synthesis of syndiotactic polystyrene: reaction mechanisms and catalysis. Prog Polym Sci 21:47–88

    Article  CAS  Google Scholar 

  5. Schellenberg J, Tomotsu N (2002) Syndiotactic polystyrene catalysts and polymerization. Prog Polym Sci 27:1925–1982

    Article  CAS  Google Scholar 

  6. Rodrigues A-S, Kirillov E, Carpentier J-F (2008) Group 3 and 4 single-site catalysts for stereospecific polymerization of styrene. Coord Chem Rev 252:2115–2136

    Article  CAS  Google Scholar 

  7. Schellenberg J (2009) Recent transition metal catalysts for syndiotactic polystyrene. Prog Polym Sci 34:688–718

    Article  CAS  Google Scholar 

  8. Schellenberg J (ed) (2009) Syndiotactic polystyrene: synthesis, characterization, processing, and applications. Wiley, New Jersey

    Google Scholar 

  9. Pellecchia C, Proto A, Zambelli A (1992) Copolymerization of styrene and isoprene: an insight into the mechanism of syndiospecific styrene polyinsertion. Macromolecules 25:4450–4452

    Article  CAS  Google Scholar 

  10. Zambelli A, Proto A, Longo P, Oliva P (1994) Binary copolymerizations of styrene and conjugated diolefins in the presence of cyclopentadienyltitanium trichloride-methylaluminoxane. Macromol Chem Phys 195:2623–2631

    Article  CAS  Google Scholar 

  11. Peluso A, Impronta R, Zambelli A (1997) Mechanism of isoprene and butadiene polymerization in the presence of CpTiCl3–MAO initiator: a theoretical study. Macromolecules 30:2219–2227

    Article  CAS  Google Scholar 

  12. Cunningham ID, Fassihi K (2005) The cyclopentadienyltitanium trichloride/MAO-catalysed polymerisation of methyl acrylate and copolymerisation with styrene and isoprene. Polym Bull 53:359–365

    Article  CAS  Google Scholar 

  13. Naga N, Imanishi Y (2003) Copolymerization of styrene and conjugated dienes with half-sandwich titanium (IV) catalysts: the effect of the ligand structure on the monomer reactivity, monomer sequence distribution, and insertion mode of dienes. J Polym Sci A 41:939–946

    Article  CAS  Google Scholar 

  14. Cugini C, Rombolà OA, Giarrusso A, Porri L, Ricci G (2005) Polymerization of 4-methyl-1, 3-pentadiene with catalysts based on cyclopentadienyl titanium chlorides: effect of anti/syn isomerism of the allylic group on the chemoselectivity and the role of backbiting coordination in 1,3-diene polymerization. Macromol Chem Phys 206:1684–1690

    Article  CAS  Google Scholar 

  15. Cuomo C, Serra MC, Gonzalez Maupoey M, Grassi A (2007) Copolymerization of styrene with butadiene and isoprene catalyzed by the monocyclopentadienyl titanium complex Ti(η5-C5H5)(η2-MBMP)Cl. Macromolecules 40:7089–7097

    Article  CAS  Google Scholar 

  16. Oliva L, Longo P, Grassi A, Ammendola P, Pellecchia C (1990) Polymerization of 1, 3-alkadienes in the presence of nickel- and titanium-based catalytic systems containing methylaluminoxane. Macromol Chem Rapid Commun 11:519–524

    Article  CAS  Google Scholar 

  17. Rodrigues A-S, Kirillov E, Vuillemin B, Razavi A, Carpentier J-F (2008) Stereo controlled styrene–isoprene copolymerization and styrene–ethylene–isoprene terpolymerization with a single-component allyl ansa-neodymocene catalyst. Polymer 49:2039–2045

    Article  CAS  Google Scholar 

  18. Rabagliati FM, Pérez MA, Soto MA, Martínez de Ilarduya A, Muñoz-Guerra S (2001) Copolymerization of styrene by diphenylzinc-additive systems. I. Copolymerization of styrene/p-tert-butylstyrene by Ph2Zn–metallocene–MAO systems. Eur Polym J 37:1001–1006

    Article  Google Scholar 

  19. Rabagliati FM, Pérez MA, Cancino RA, Soto MA, Rodríguez FJ, Caro CJ (2003) Styrene copolymerization using diphenylzinc-additive initiator systems: styrene/p-substituted styrenes. Macromol Symp 192:13–23

    Article  CAS  Google Scholar 

  20. Pérez MA, Caro CJ, Cancino RA, Rabagliati FM (2003) Ph2Zn–metallocene–MAO initiator systems in the homo- and copolymerization of styrene/p-alkylstyrene. Polym Bull 51:199–208

    Article  Google Scholar 

  21. Rabagliati FM, Pérez MA, Rodríguez FJ, Caro CJ, Crispel N (2005) Further studies on styrene/styrene derivative copolymerizations using combined diphenylzinc-additive initiator systems. Polym Int 54:437–441

    Article  CAS  Google Scholar 

  22. Rabagliati FM, Rodríguez FJ, Alla A, Muñoz-Guerra S (2006) Styrene-substituted-styrene copolymerization using diphenyl zinc-metallocene-methylaluminoxane systems. Polym Int 55:910–915

    Article  CAS  Google Scholar 

  23. Rabagliati FM, Cancino RA, Rodríguez FJ (2001) Copolymerization of styrene by diphenylzinc-additive systems. Part II: copolymerization of styrene/1-alkene by Ph2Zn–metallocene–MAO systems. Polym Bull 46:427–434

    Article  CAS  Google Scholar 

  24. Rabagliati FM, Cancino RA, Pérez MA, Rodríguez FJ (2004) Styrene/(styrene derivative) and styrene/(1-alkene) copolymerization using Ph2Zn—additive initiator systems. Macromol Symp 216:55–64

    Article  CAS  Google Scholar 

  25. Cancino RA, Rodríguez FJ, Pérez MA, Rabagliati FM (2005) Styrene/(1-alkene) copolymerization by CpTiCl3—additive initiator systems. J Chil Chem Soc 50:427–430

    Article  CAS  Google Scholar 

  26. Rabagliati FM, Cancino RA, Martínez de Ilarduya A, Muñoz-Guerra S (2005) Homo- and copolymerization of styrene and 1-alkene using Ph2Zn–Et(Ind)2ZrCl2–MAO initiator systems. Eur Polym J 41:1013–1019

    Article  CAS  Google Scholar 

  27. Rabagliati FM, Rodríguez FJ, Alla A, Martínez de Ilarduya A, Muñoz-Guerra S (2007) Styrene/(substituted styrene) copolymerization by Ph2Zn–metallocene–MAO systems: synthesis and characterization of poly(styrene-co-p-hydroxystyrene) copolymers. Polymer 48:4646–4652

    Article  CAS  Google Scholar 

  28. Solomon OF, Gotesman W (1967) Calculation of viscosity number from a single measurement. Makromol Chem 104:177–184

    Article  CAS  Google Scholar 

Download references

Acknowledgments

Financial support by the Fondo Nacional de Desarrollo Científico y Tecnológico (FONDECYT) under Project 108-5061 is gratefully acknowledged. The authors thank Dr. Francisco J. Rodríguez of the Laboratorio Envases, Laben-Chile (USACH) for the DSC analyses and Dr. Juan del C. Guerrero of the Facultad de Química y Biología (USACH) for measurement of NMR spectra. Thanks are due to Dr. Antxon Martínez de Ilarduya, of the Universidad Politécnica de Catalunya, Barcelona, Spain, for discussion and advise on NMR spectra.

Author information

Authors and Affiliations

  1. Grupo Polímeros, Departamento Ciencias del Ambiente, Facultad de Química y Biología, Universidad de Santiago de Chile, Casilla 40, Correo 33, Santiago, Chile

    F. M. Rabagliati & L. A. Muñoz

  2. Departamento de Ingeniería Química y Biotecnología, Facultad de Ciencias Físicas y Matemáticas, and Centro para la Investigación Avanzada de Materiales (CIMAT), Universidad de Chile, Casilla 2777, Santiago, Chile

    R. Quijada

Authors
  1. F. M. Rabagliati
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. L. A. Muñoz
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. R. Quijada
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to F. M. Rabagliati.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Rabagliati, F.M., Muñoz, L.A. & Quijada, R. Styrene copolymerization using a metallocenic initiator. Homo- and copolymerization of styrene with isoprene through zirconocene–MAO initiating systems. Polym. Bull. 67, 1425–1434 (2011). https://doi.org/10.1007/s00289-011-0457-4

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00289-011-0457-4

Keywords

Search

Navigation