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.

Functional Polymers and Polymeric Materials From Renewable Alpha-Unsaturated Gamma-Butyrolactones

“…The copolymerization reactivity ratios were higher for MBL compared to the comonomers. Similarly, higher copolymerization reactivity ratios were found also for MBL derivatives, γ-MMBL and β-MMBL, during their copolymerization with styrene and MMA (Pittman and Lee, 2003;Cockburn et al, 2010) and n-butyl acrylate (BA) (Cockburn et al, 2011). In addition to batch copolymerizations, a γ-MMBL was successfully used also in copolymerization with styrene in miniemulsion (Qi et al, 2008) and using stabilizer-free precipitation either in water (Qi et al, 2008) or in isoamyl acetate (Ramram et al, 2016) to form polymeric particles of size in the range of 50-200 or 600-2600 nm, respectively.…”

Sustainable Polymers from Biomass‐Derived α‐Methylene‐γ‐Butyrolactones

“…The study of the free-radical copolymerizations of γ MMBL (M1) with M2, including styrene, MMA, and n-butyl acrylate (nBA), has found that, when (24) compared to MMA, γ MMBL is preferentially incorporated into copolymers when copolymerized with styrene, MMA, and nBA (44). The monomer reactivity ratios fit from bulk copolymerizations of γ MMBL with styrene, MMA, and nBA are r 1 = 0.80 ± 0.04 and r 2 = 0.34 ± 0.04 (styrene), r 1 = 3.0 ± 0.3 and r 2 = 0.33 ± 0.01 (MMA), and r 1 = 7.0 ± 2.0 and r 2 = 0.16 ± 0.03 (nBA), respectively.…”

“…The polymerization of γ MMBL has not been studied extensively as compared to MBL; nevertheless, it has also been polymerized by free-radical emulsion polymerization (16,41) as well as radical, anionic, and GTP methods (42). Free-radical copolymerizations of γ MMBL with MMA and styrene have been investigated in detail through photoinitiation using the pulsed-laser polymerization/size-exclusion chromatography technique (43,44). Recently reported literature for the polymerization of γ MMBL included coordination polymerization with metallocene complexes (36,45), half-sandwich indenyl rare-earth metal dialkyls (46), ansarare-earth metal catalysts (27), and group 4 nonmetallocene benzyl complexes (47); GTP with bifunctional silicon propagators (48) and dinuclear silyliumenolate bifunctional catalysts (49); anionic polymerization with potassium salts (KH/Al(C 6 F 5 ) 3 ) (50); and zwitterionic polymerization with N-heterocyclic carbenes (51) and alane-based classical and frustrated Lewis pairs (52,53).…”

A Combined Computational and Experimental Study of Copolymerization Propagation Kinetics for 1‐Ethylcyclopentyl methacrylate and Methyl methacrylate

“…The IPUE model in conjunction with pulsed‐laser polymerization/size‐exclusion chromatography (PLP/SEC) has been successfully applied to characterize quite a few binary copolymer systems . However, the underlying assumptions of IPUE are not always strictly obeyed.…”