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Kinetics of the Anionic Ring Opening Polymerization of Cyclosiloxanes Initiated with a Superbase

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Abstract

Kinetics of the anionic ring opening polymerization of octamethylcyclotetrasiloxane, D4, and hexamethylcyclotrisiloxane, D3, in toluene solution initiated by hexapyrrolidinediphosphazenium hydroxide, P2Pyr6 +OH− were studied. Reactions are first order both in monomer and in initiator. The specific rate of the D3 polymerization is higher than that of D4 by about 2–3 orders of magnitudes. Activation energies are 18.1 kcal mol−1 for D4 and 11 kcal mol−1 for D3. The back-biting reaction leading to decamethylcyclopentasiloxane, D5, was followed in the polymerization of D4. This reaction is retarded by the presence of monomer. The kinetics is interpreted in terms of a mechanism in which the active propagation center appears mostly as a monomer separated ion pair, which is also the intermediate in the propagation step.

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Authors and Affiliations

  1. Center of Molecular and Macromolecular Studies of the Polish Academy of Sciences, Sienkiewicza 112, 90-363, tódź, Poland

    Agnieszka Grzelka, Julian Chojnowski & Witold Fortuniak

  2. Dow Corning Ltd, Cardiff Road, Barry, South Glamorgan, Wales, CF63 2YL, UK

    Richard G. Taylor & Peter C. Hupfield

Authors
  1. Agnieszka Grzelka
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  2. Julian Chojnowski
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  3. Witold Fortuniak
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  4. Richard G. Taylor
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  5. Peter C. Hupfield
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Correspondence to Julian Chojnowski.

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Grzelka, A., Chojnowski, J., Fortuniak, W. et al. Kinetics of the Anionic Ring Opening Polymerization of Cyclosiloxanes Initiated with a Superbase. Journal of Inorganic and Organometallic Polymers 14, 85–99 (2004). https://doi.org/10.1023/B:JOIP.0000028088.53201.f7

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  • DOI: https://doi.org/10.1023/B:JOIP.0000028088.53201.f7

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