Thermal dissociation behavior of polymers with hemiacetal ester moieties in the side chain: The effect of structure on dissociation temperature

Radical polymerization of ‘dehydroaspirin’ with the formation of a hemiacetal ester skeleton: a hint for recyclable vinyl polymers

“…Therefore, MBDO has higher reactivity than VAc. The vinyl polymerization of MBDO generates a hemiacetal ester skeleton that can be cleaved by heat [37][38][39][40] and Brønsted 32 or Lewis 41 acids. However, the DTA curve acquired from poly(MBDO) did not exhibit any peaks [Figure 3(a)], prior to the onset of mass loss (T d ) at 232 °C, while the glass transition temperature (T g ) was observed at 132 °C in DSC curve [Figure 3(b)].…”

Hemiacetal Ester Exchanges, Study of Reaction Conditions and Mechanistic Pathway

“…In particular, hemiacetal esters spontaneously dissociate into carboxylic acids and vinyl ethers upon heating. This thermal dissociation has been demonstrated to be structure-dependent by Otsuka et al [4][5][6]. In a first publication [4], they showed that hemiacetals formed from carboxylic acids bearing unsaturated groups have a lower dissociation temperature than their saturated aliphatic analogs due to inductive and mesomeric electronic effects.…”

α‐exomethylene lactone possessing acetal–ester linkage: Polymerization and postpolymerization modification for water‐soluble polymer

“…Among them, a simple example, 2,6‐dimethyl‐5‐methylene‐1,3‐dioxa‐4‐one (DMDO) can be synthesized via Bailys–Hilman reaction of phenyl acrylate, but no application in polymer chemistry are reported. As well known, A–E linkage is a dynamic covalent bond, which is readily converted to carboxyl and hydroxyl groups by acid hydrolysis, while the thermal decomposition affords a carboxylic acid and a vinyl ether . In fact, polymers with A–E linkage in their side groups and backbones have been reported as degradable polymeric materials.…”

“…As well known, A–E linkage is a dynamic covalent bond, which is readily converted to carboxyl and hydroxyl groups by acid hydrolysis, while the thermal decomposition affords a carboxylic acid and a vinyl ether . In fact, polymers with A–E linkage in their side groups and backbones have been reported as degradable polymeric materials. Similarly, DMDO is expected to afford water‐soluble polymer ( P2 ) with hydroxyl and carboxylic groups in the pendant groups via vinyl polymerization followed by acid hydrolysis (Scheme ), while the ROP may result a degradable polyester.…”