Skip to main content
SpringerLink
Log in

Chain transfer to monomer and polymer in the radical polymerization of vinyl neo-decanoate

  • Published:
Macromolecular Research Aims and scope Submit manuscript

Abstract

Molecular weight distributions of poly(vinylneo-decanoate) produced by the bulk polymerization of the monomer to low conversions were investigated to obtain values of the rate constants for the chain transfer to monomer (CM). The value ofC M of 7.5 (± 0.6)× 10−4 was obtained from a logarithmic plot of the number distribution at 5, 25, and 50°C, which suggests that the activation energy for chain transfer is on the order of 20–25 kJ mol−1. These plots were linear between the number and weight-average degrees of polymerization, but not over the whole molecular weight range for which a significant signal was observed in the gel permeation chromatography (GPC) trace. Modeling suggests that the deviations observed at high molecular weights can be explained by branching of the chains through chain transfer to the polymer, with a branching density as low as 10−5, without affecting the slope at low values of the number of monomer unit,N. This deviation from the expected distribution of linear chains was used to estimate the branching densities at low conversion.

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

Similar content being viewed by others

References

  1. A. J. Buselli, M. K. Lindemann, and C. E. Blades,J. Polym. Chem.,28, 485 (1958).

    CAS  Google Scholar 

  2. J. Brandrup, E. H. Immergut, and E. A. Grulke, Eds.,Polymer Handbook, John Wiley & Sons, New York, 1999.

    Google Scholar 

  3. P. A. Clay and R. G. Gilbert,Macromolecules,28, 552 (1995).

    Article  CAS  Google Scholar 

  4. G. Moad and C. L. Moad,Macromolecules,29, 7727 (1996).

    Article  CAS  Google Scholar 

  5. J. P. A. Heuts, T. P. Davis, and G. T. Russell,Macromolecules,32, 6019 (1999).

    Article  CAS  Google Scholar 

  6. R. Balic, R. G. Gilbert, M. D. Zammit, T. P. Davis, and C. M. Miller,Macromolecules,30, 3775 (1997).

    Article  CAS  Google Scholar 

  7. R. A. Hutchinson, D. A. Paquet, J. H. McMinn, S. Beuermann, R. E. Fuller, and C. Jackson,DECHEMA Monographs,131, 467 (1995).

    CAS  Google Scholar 

  8. D. W. Shortt,J. Liquid Chromat.,16, 3371 (1993).

    Article  CAS  Google Scholar 

  9. S. Maeder and R. G. Gilbert,Macromolecules,31, 4410 (1998).

    Article  CAS  Google Scholar 

  10. D. F. Sangster, J. Feldthusen, J.Strauch, M. Steng, C. M.Fellows, and R. G. Gilbert, to be submitted 2004.

  11. M. F. Cunningham, K. Geramita, and J. W. Ma,Polymer,41, 5385 (2000).

    Article  CAS  Google Scholar 

  12. H. De Bruyn, PhD Thesis, Sydney University, Sydney, 1998.

  13. H. Scholten, J. Vermeulen, and V. Westrenen,Polym. Paint Colour J.,178, 852 (1988).

    CAS  Google Scholar 

  14. H. Scholten and C. Reader,First Asia-Pacific Conference on Advances in Coatings Technology, Singapore, 1991.

  15. N. Subramaniam, PhD Thesis, University of Sydney, Sydney, 1999.

  16. J. A. Kerr, Ed.,Rate Processes in the Gas Phase, Wiley Interscience, New York, 1973.

    Google Scholar 

  17. R. A. Hutchinson, J. R. Richards, and M. T. Aronson,Macromolecules,27, 4530 (1994).

    Article  CAS  Google Scholar 

  18. M. Stickler and G. Meyerhoff,Makromol. Chem.,179, 2729 (1978).

    Article  CAS  Google Scholar 

  19. P. A. Clay, R. G. Gilbert, and G. T. Russell,Macromolecules,30, 1935 (1997).

    Article  CAS  Google Scholar 

  20. A. Ghielmi, S. Florentino, G. Storti, M. Mazzotti, and M. Morbidelli,J. Polym. Sci.; Part A: Polym. Chem.,35, 827 (1997).

    Article  CAS  Google Scholar 

  21. S. Thomas, A. E. Hamielec, and J. Soares,Polym. React. Eng.,5, 183 (1997).

    CAS  Google Scholar 

  22. C. H. Bamford and H. Tompa,J. Polym. Sci.,10, 345 (1952).

    Article  Google Scholar 

  23. C. Sayer, P. H. H. Araujo, G. Arzamendi, J. M. Asua, E. L. Lima, and J. C. Pinto,J. Polym. Sci.: Part A; Polym. Chem.,39, 3513 (2001).

    Article  CAS  Google Scholar 

  24. H. Tobita,J. Polym. Sci.: Part B; Polym. Phys.,39, 391 (2001).

    Article  CAS  Google Scholar 

  25. H. Tobita,Polymer,35, 3023 (1994).

    Article  CAS  Google Scholar 

  26. H. Tobita,Acta Polym.,46, 185 (1995).

    Article  CAS  Google Scholar 

  27. P. J. Flory,Principles of Polymer Chemistry, Cornell University Press, Ithaca, 1953.

    Google Scholar 

  28. N. M. Ahmad, F. Heatley, and P. A. Lovell,Macromolecules,31, 2822 (1998).

    Article  CAS  Google Scholar 

  29. A. E. Hamielec, inSynthesis, Kinetics, and Characterization of Poly(vinyl acetate), M. S. El-Aasser and J. W. Vanderhoff, Eds., Applied Science Publishers, London, 1981.

    Google Scholar 

  30. D. Britton, F. Heatley, and P. A. Lovell,Macromolecules,31, 2828 (1998).

    Article  CAS  Google Scholar 

  31. W. W. Graessley, R. D. Hartung, and W. C. Uy,J. Polym. Sci.,A2, 1919 (1969).

    Google Scholar 

  32. F. W. Billmeyer,Textbook of Polymer Science, Wiley-Interscience, New York, 1962.

    Google Scholar 

Download references

Author information

Author notes

  1. Christopher M. Fellows

    Present address: School of Biological, Biomedical, and Molecular Sciences, University of New England, 2351, Armidale, NSW, Australia

Authors and Affiliations

  1. Key Centre for Polymer Colloids, School of Chemistry, University of Sydney, 2006, Sydney, NSW, Australia

    Robert Balic & Christopher M. Fellows

  2. Department of Polymer Chemistry and Technology, Eindhoven University of Technology, P.O. Box 513, MB 5600 MB, Eindhoven, The Netherlands

    Alex M. van Herk

Authors
  1. Robert Balic
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Christopher M. Fellows
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Alex M. van Herk
    View author publications

    You can also search for this author in PubMed Google Scholar

Rights and permissions

Reprints and permissions

About this article

Cite this article

Balic, R., Fellows, C.M. & van Herk, A.M. Chain transfer to monomer and polymer in the radical polymerization of vinyl neo-decanoate. Macromol. Res. 12, 325–335 (2004). https://doi.org/10.1007/BF03218408

Download citation

  • Received:

  • Revised:

  • Issue Date:

  • DOI: https://doi.org/10.1007/BF03218408

Keywords

Search

Navigation