Free radical copolymerization kinetics of γ-methyl-α-methylene-γ-butyrolactone (MeMBL)

Biomacromolecules. 2011 Jun 13;12(6):2319-26. doi: 10.1021/bm200400s. Epub 2011 May 10.

Abstract

The propagation kinetics and copolymerization behavior of the biorenewable monomer γ-methyl-α-methylene-γ-butyrolactone (MeMBL) are studied using the pulsed laser polymerization (PLP)/size exclusion chromatography (SEC) technique. The propagation rate coefficient for MeMBL is 15% higher than that of its structural analogue, methyl methacrylate (MMA), with a similar activation energy of 21.8 kJ·mol(-1). When compared to MMA, MeMBL is preferentially incorporated into copolymers when reacted with styrene (ST), MMA, and n-butyl acrylate (BA); the monomer reactivity ratios fit from bulk MeMBL/ST, MeMBL/MMA, and MeMBL/BA copolymerizations are r(MeMBL) = 0.80 ± 0.04 and r(ST) = 0.34 ± 0.04, r(MeMBL) = 3.0 ± 0.3 and r(MMA) = 0.33 ± 0.01, and r(MeMBL) = 7.0 ± 2.0 and r(BA) = 0.16 ± 0.03, respectively. In all cases, no significant variation with temperature was found between 50 and 90 °C. The implicit penultimate unit effect (IPUE) model was found to adequately fit the composition-averaged copolymerization propagation rate coefficient, k(p,cop), for the three systems.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • 4-Butyrolactone / analogs & derivatives*
  • 4-Butyrolactone / chemical synthesis
  • Acrylates / chemistry
  • Chromatography, Gel
  • Free Radicals
  • Green Chemistry Technology / methods*
  • Kinetics
  • Lasers
  • Methylmethacrylate / chemistry*
  • Models, Chemical
  • Polymerization
  • Polymers / chemical synthesis*
  • Styrene / chemistry*
  • Temperature
  • Thermodynamics
  • Viscosity

Substances

  • Acrylates
  • Free Radicals
  • Polymers
  • Methylmethacrylate
  • alpha-methylene gamma-butyrolactone
  • Styrene
  • n-butyl acrylate
  • 4-Butyrolactone