SpringerLink
Log in

Thermal decomposition of 3,3,6,6,9,9-hexaethyl-1,2,4,5,7,8-hexaoxacyclononane in solution and its use in methyl methacrylate polymerization

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

Abstract

The kinetics of the thermal decomposition reaction of diethylketone triperoxide (3,3,6,6,9,9-hexaethyl-1,2,4,5,7,8-hexaoxacyclononane, DEKTP) in ethylbenzene solution were studied in the temperature range of 120.0–150.0 °C and at an initial concentration range of 0.01–0.10 M. This peroxide was used as a new initiator in methyl methacrylate (MMA) polymerization process at high temperatures (110.0–140.0 °C) in ethylbenzene solution. The effects of initiator concentration and reaction temperature on the polymerization rate were investigated in detail. Thus, activation parameters of the solution polymerization process (ΔE d* = 83.3 kJ mol−1 and ΔE p* − ΔE t*/2 = 54.0 kJ mol−1) will be obtained. DEKTP can effectively act as initiator in MMA polymerization and its performance is similar to that presented by a multifunctional initiator resulting in high-molecular weight polymethylmethacrylate with a high reaction rate.

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

Access this article

Log in via an institution

Subscribe and save

Springer+ Basic
EUR 32.99 /Month
  • Get 10 units per month
  • Download Article/Chapter or Ebook
  • 1 Unit = 1 Article or 1 Chapter
  • Cancel anytime
Subscribe now

Buy Now

Price includes VAT (Germany)

Instant access to the full article PDF.

Institutional subscriptions

Scheme 1
Scheme 2
Fig. 1
Fig. 2
Scheme 3
Scheme 4
Fig. 3
Fig. 4
Fig. 5

Similar content being viewed by others

References

  1. Sheng W, Shan G, Huang Z, Weng Z, Pan Z (2005) Decomposition of 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy) hexane and its use in polymerization of styrene and methyl methacrylate. Polymer 46:10553–10560

    Article  CAS  Google Scholar 

  2. Scorah MJ, Dhib R, Penlidis A (2005) Use of a novel tetrafunctional initiator in the free radical homo- and copolymerization of styrene, methyl methacrylate and α-methyl styrene. J Macromol Sci Pure Appl Chem 42:403–426

    Article  Google Scholar 

  3. Sheng W, Wu J, Shan G, Huang Z, Weng Z (2004) Free-radical bulk polymerization of styrene with a new trifunctional cyclic peroxide initiator. J Appl Polym Sci 94:1035–1042

    Article  CAS  Google Scholar 

  4. Cerna J, Morales G, Eyler GN, Cañizo AI (2002) Bulk polymerization of styrene catalyzed by bi- and trifunctional cyclic initiators. J Appl Polym Sci 83:1–11

    Article  CAS  Google Scholar 

  5. Cafferata LFR, Eyler GN, Svaltman EL, Cañizo AI, Alvarez EE (1991) Solvent effects in the thermal decomposition reactions of cyclic ketone diperóxidos. J Org Chem 56:411–414

    Article  CAS  Google Scholar 

  6. Eyler GN (2006) Kinetic solvent effects on the thermal decomposition reaction of acetone triperóxido. J Phys Org Chem 19:776–779

    Article  CAS  Google Scholar 

  7. Cañizo AI (2006) Cyclic diethylketone triperoxide: preparation, kinetic in solution, solvent effect and its applications in polymerization processes. Trends Org Chem 11:55–64

    Google Scholar 

  8. Lockley JE, Ebdon JR, Rimmer S, Tabner BJ (2001) Polymerization of methyl methacrylate initiated by ozonates of tetramethylethene. Polymer 42:1797–1807

    Article  CAS  Google Scholar 

  9. Barreto GP, Eyler GN (2007) Radicalary polymerization of methyl methacrylate in ethylbenzene solution using diethylketone triperoxide as multifunctional initiator. Mol Med Chem 12:25–27

    Google Scholar 

  10. Eyler GN, Cañizo AI, Alvarez EE, Cafferata LFR (1993) Improved procedure for the preparation of diethyl ketone triperoxide and kinetics of its thermal decomposition reaction in solution. Tetrahedron Lett 34:1745–1746

    Article  CAS  Google Scholar 

  11. Cañizo AI, Eyler GN, Morales G, Cerna J (2004) Diethyl ketone triperoxide: thermal decomposition reaction in chlorobenzene solution and its application as initiator of polymerization. J Phys Org Chem 17:215–220

    Article  Google Scholar 

  12. Cafferata LFR, Eyler GN, Mirífico MV (1984) Kinetics and mechanism of acetone cyclic diperoxide (3,3,6,6-tetramethyl-1,2,4,5-tetraoxane) thermal decomposition in benzene solution. J Org Chem 49:2107–2111

    Article  CAS  Google Scholar 

  13. Brandrup J, Immergut EH, Grulke EA (1999) Polymer handbook, 4th edn. Wiley Interscience, New York

    Google Scholar 

  14. García FC (2000) Estudio de Polímeros Acrílicos y Metacrílicos derivados de la Glicerina: Síntesis y Propiedades de Transporte. Doctoral Thesis, Universidad de Burgos, Burgos, Spain

Download references

Acknowledgments

This research was financially supported by the Universidad Nacional del Centro de la Provincia de Buenos Aires (UNCPBA). G.P.B. is a fellowship holder of the Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET).

Author information

Authors and Affiliations

  1. Laboratorio de Química, Dpto. Ingeniería Química, Facultad de Ingeniería, Universidad Nacional del Centro de la Provincia de Buenos Aires, Avda. del Valle 5737, B7400JWI, Olavarría, Buenos Aires, Argentina

    Gastón P. Barreto & Gladys N. Eyler

Authors
  1. Gastón P. Barreto
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Gladys N. Eyler
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Gastón P. Barreto.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Barreto, G.P., Eyler, G.N. Thermal decomposition of 3,3,6,6,9,9-hexaethyl-1,2,4,5,7,8-hexaoxacyclononane in solution and its use in methyl methacrylate polymerization. Polym. Bull. 67, 1–14 (2011). https://doi.org/10.1007/s00289-010-0348-0

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00289-010-0348-0

Keywords

Search

Navigation