title: Free radical copolymerization kinetics of γ-methyl-α-methylene-γ-butyrolactone (MeMBL).
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.
authors.affiliation: Department of Chemical Engineering, Queen's University , Kingston, Ontario K7L 3N6, Canada.
authors.forename: Robert A
authors.initials: RA
authors.lastname: Cockburn
authors.forename: Rebekka
authors.initials: R
authors.lastname: Siegmann
authors.forename: Kevin A
authors.initials: KA
authors.lastname: Payne
authors.forename: Sabine
authors.initials: S
authors.lastname: Beuermann
authors.forename: Timothy F L
authors.initials: TF
authors.lastname: McKenna
authors.forename: Robin A
authors.initials: RA
authors.lastname: Hutchinson
mesh_terms: D015107:4-Butyrolactone / Q000031:analogs & derivatives* / Q000138:chemical synthesis; D000179:Acrylates / Q000737:chemistry; D002850:Chromatography, Gel; D005609:Free Radicals; D055772:Green Chemistry Technology / Q000379:methods*; D007700:Kinetics; D007834:Lasers; D020366:Methylmethacrylate / Q000737:chemistry*; D008956:Models, Chemical; D058105:Polymerization; D011108:Polymers / Q000138:chemical synthesis*; D020058:Styrene / Q000737:chemistry*; D013696:Temperature; D013816:Thermodynamics; D014783:Viscosity
chemical_list: D000179:Acrylates; D005609:Free Radicals; D011108:Polymers; D020366:Methylmethacrylate; C014096:alpha-methylene gamma-butyrolactone; D020058:Styrene; C032490:n-butyl acrylate; D015107:4-Butyrolactone