Methylenelactide: vinyl polymerization and spatial reactivity effects

Abstract

The first detailed study on free-radical polymerization, copolymerization and controlled radical polymerization of the cyclic push–pull-type monomer methylenelactide in comparison to the non-cyclic monomer α-acetoxyacrylate is described. The experimental results revealed that methylenelactide undergoes a self-initiated polymerization. The copolymerization parameters of methylenelactide and styrene as well as methyl methacrylate were determined. To predict the copolymerization behavior with other classes of monomers, Q and e values were calculated. Further, reversible addition fragmentation chain transfer (RAFT)-controlled homopolymerization of methylenelactide and copolymerization with N,N-dimethylacrylamide was performed at 70 °C in 1,4-dioxane using AIBN as initiator and 2-(((ethylthio)carbonothioyl)thio)-2-methylpropanoic acid as a transfer agent.

Production and Polymerization of Biobased Acrylates and Analogs

“…Later, the same authors published a complementary study on the kinetics of free‐radical and RAFT‐mediated MLA polymerization, as well as its copolymerization with styrene, MMA, and N , N ‐dimethylacrylamide. [ 447 ] The reactivity of MLA was found to be similar to that of MMA. However, it was observed that MLA could self‐initiate its polymerization in AIBN‐free experiments.…”

Syntheses and chemical transformations of glycolide and lactide as monomers for biodegradable polymers

“…57). A detailed mechanism of radical polymerization of exo-methylene lactide is described by Britner and Ritter [307], which explains the formation of isotactic, syndiotactic, and atactic poly-exo-methylene lactides (Fig. 58).…”

Novel Poly(Methylenelactide-g-L-Lactide) Graft Copolymers Synthesized by a Combination of Vinyl Addition and Ring-Opening Polymerizations

“…Recently, Britner and Ritter [ 58 , 59 ] reinvestigated Scheibelhoffer’s first study of a radical polymerizable lactide derivative with respect to polymerization and polymer analogous aminolysis under mild conditions. In this work, the optically active MLA was polymerized by free radical polymerization in solution using AIBN as an initiator and resulted in isotactic-biased atactic optically active poly(methylenelactide) (PMLA) with molecular weights ranging between 4 × 10 4 –1 × 10 5 g mol −1 with dispersity, Đ ~2.5 and a T g of 244 °C.…”

“…According to previous works, PMLA has poor solubility, sluggish dissolution, and that it is challenging to handle the polymer as a melt for polymerization. As previously mentioned, Britner et al [ 58 , 59 ] have found a way to overcome this challenge by PMLA functionalization. In the underlying study, Britner and Ritter focused on spatial effects with respect to interactions between neighboring lactide rings.…”

“…Moreover, it was found that the PMLA attached lactide rings react like activated esters and thus readily undergo quantitative amidation reactions with aliphatic primary amines under mild conditions. However, up to present, no information on the copolymerization of MLA and LLA via the ROP has been reported [ 54 , 55 , 56 , 58 , 59 , 60 , 61 , 62 ].…”