Radical Copolymerization Kinetics of Bio-Renewable Butyrolactone Monomer in Aqueous Solution

Abstract

Abstract:The radical copolymerization kinetics of acrylamide (AM) and the water-soluble monomer sodium 4-hydroxy-4-methyl-2-methylene butanoate (SHMeMB), formed by saponification of the bio-sourced monomer γ-methyl-α-methylene-γ-butyrolactone (MeMBL), are investigated to explain the previously reported slow rates of reaction during synthesis of superabsorbent hydrogels. Limiting conversions were observed to decrease with increased temperature during SHMeMB homopolymerization, suggesting that polymerization rate is limited by depropagation. Comonomer composition drift also increased with temperature, with more AM incorporated into the copolymer due to SHMeMB depropagation. Using previous estimates for the SHMeMB propagation rate coefficient, the conversion profiles were used to estimate rate coefficients for depropagation and termination (k t ). The estimate for k t,SHMeMB was found to be of the same order of magnitude as that recently reported for sodium methacrylate, with the averaged copolymerization termination rate coefficient dominated by the presence of SHMeMB in the system. In addition, it was found that depropagation still controlled the SHMeMB polymerization rate at elevated temperatures in the presence of added salt.

Initiated Chemical Vapor Deposition (iCVD) of Bio-Based Poly(tulipalin A) Coatings: Structure and Material Properties

“…Butyrolactone sustainable polymers have been previously synthesized via a wide range of free-radical polymerization (FRP) techniques, such as conventional FRP [ 11 , 12 , 13 , 14 , 15 , 16 ], atom-transfer radical polymerization (ATRP) [ 17 ], and reversible-addition fragmentation chain transfer (RAFT) [ 5 , 18 , 19 , 20 ]. Despite the interesting and unique properties of those monomers and their polymers, their polymerization studies are still relatively scarce in the literature and were mainly carried out in highly toxic organic solvents to produce bulk polymers, at low monomer conversions [ 5 ].…”

Surfactant-Free Peroxidase-Mediated Enzymatic Polymerization of a Biorenewable Butyrolactone Monomer via a Green Approach: Synthesis of Sustainable Biobased Latexes

“…Alongside butyrolactones being attractive candidates in replacing monomers of fossil fuel origin, from a synthetic standpoint, they have been synthesized via a cost-effective method from itaconic acid (IA), which is a biomass intermediate produced from the fermentation of corn or rice. − One of those monomers (MMBL) is currently being produced commercially at a large scale from levulinic acid (a biomass intermediate) via a two-step catalytic process . The biobased/sustainable polymers produced from γ-butyrolactone monomers have in turn been synthesized via free-radical polymerization techniques. ,− Nevertheless, such studies are scarce and are constrained by limitations. One of the drawbacks is that the majority utilize toxic organic solvents and provide low polymer yields .…”

“…Interestingly, biorenewable monomers based on a five-membered γ-butyrolactone ring (Figure a) represent natural and potential alternatives to fossil fuel monomers. − Those monomers are exocyclic analogues of methyl methacrylate (MMA) and exhibit interesting and unique properties as they have dual functionality (possess a vinyl group and a lactone ring), where the vinyl moiety can be polymerized via free-radical polymerization, while the lactone ring can be polymerized via ring opening. Significantly, the associated polymers demonstrate a glass-transition temperature ( T g ) that is twice that of PMMA (i.e., T g ∼ 100 °C), thereby rendering them suitable for potential applications at elevated temperatures …”