Methyl methacrylate polymerization in nanoporous confinement

Haoyu Zhao, Sindee L. Simon

Research output: Contribution to journalArticlepeer-review

46 Scopus citations


The effect of nanoconfinement on the rate of isothermal polymerization of methyl methacrylate (MMA) polymerization is investigated using differential scanning calorimetry. Controlled pore glass (CPG) with pore diameters of 13, 50, and 111 nm are used for the confinement of the reaction. Both hydrophilic and hydrophobic pore surfaces are studied. The effective reaction rate and the apparent activation energy at low conversions, prior to autoacceleration, are unchanged in hydrophobic pores. On the other hand, in hydrophilic pores, the reaction rate increases by as much as a factor of 8 in the smallest 13 nm hydrophilic pores, and the effective activation energy decreases. For both pore surfaces, the time required to reach autoacceleration decreases with decreasing pore size, with the effect much more pronounced in the hydrophilic pores. The results are consistent with a model of nanoconfined free radical polymerization which accounts for suppressed termination due to a decrease in the diffusivity of nanoconfined chains.

Original languageEnglish
Pages (from-to)4093-4098
Number of pages6
Issue number18
StatePublished - Aug 18 2011


  • Free radical polymerization
  • Nanoconfinement
  • PMMA


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