Journal
MACROMOLECULES
Volume 53, Issue 10, Pages 3994-4011Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.macromol.0c00207
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- A*STAR [A1786a0030]
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Poly(alkyl)acrylates are a major class of nonbiodegradable polymers which are difficult to recycle due to an all-carbon backbone. Introducing a certain number of ester bonds in the backbone via radical ring opening copolymerization of acrylates with 2-methylene-1,3 dioxepane (MDO) improves its degradability and may be promising for chemical recycling. The current work examines the influence of monomer addition profiles on the copolymerization of acrylates with MDO. We improved the homogeneity of the MDO insertion through a semibatch approach, which was demonstrated by the molecular weight distribution of fragments after alkali degradation. By detailed NMR analysis, we identified the incorporation of MDO ring retained units, formation of branches on acrylate units, and formation of branches on MDO ring open units as the key side reactions. Theoretical calculations showed that mainly kinetic factors influence the outcome of the polymerization.
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