Heteroatom-containing degradable polymers by ring-opening metathesis polymerization

Biomass-Derived Degradable Polymers via Alternating Ring-Opening Metathesis Polymerization of Exo-Oxanorbornenes and Cyclic Enol Ethers

“…The rapid advances in ring-opening metathesis polymerization (ROMP) techniques have unlocked the access to a variety of degradable and depolymerizable polymers. − This can be enabled by the rational design of cyclic alkene monomers that contain degradable functional groups such as acetal, − ester, , carbonate, silyl ether, phosphoramidate, , phosphoester, and enol ether. − Among those degradable cyclic olefin monomers, 2,3-dihydrofuran (DHF), a biomass-derived and five-membered cyclic enol ether, has recently received significant interest due to its commercial availability and unique ROMP reactivity that allows for its alternating ring-opening metathesis polymerization (AROMP) with a series of comonomers. − ,, To date, DHF has been employed in copolymerization with norbornenes, fluorinated norbornenes, diynes, enynes, and very recently endo-oxanorbornenes, to generate a diverse set of acid-degradable poly­(enol ether)­s.…”

Ring-Opening Polymerization of Lactones to Prepare Closed-Loop Recyclable Polyesters

“…Reineke and co-workers reported the synthesis and polymerization of a novel disubstituted valerolactone, β-acetoxy-δ-methyl­valerolactone, which was derived from the renewable feedstock triacetic acid lactone (TAL). The ROP thermodynamic behavior was examined, and the resultant amorphous material displayed a T g of 25 °C (Table , run 15). Li et al prepared a series of poly­(ester–amide)­s (PEAs) by the ROP of morpholino-2,5-dione derivatives (MDs), which can be synthesized from α-hydroxy acids and α-amino acids. , These amorphous PEAs can also be directly depolymerized to pristine MDs under an amberlyst 15 ion-exchange resin.…”

“…173 Recently, the incorporation of heteroatoms into the polymer backbone has become an efficient tool to accelerate degradation and construct chemical recyclable polyesters. 174 For example, Wang et al have been engaged in investigation of ROP of 1,4-dioxan-2-one (pDO) to produce degradable and chemical recyclable (co)polyesters over ten years. pDO is a six-membered lactone bearing an ether moiety.…”

Covalent connections between metal–organic frameworks and polymers including covalent organic frameworks

“…The presence of heteroatoms in polymers can modify the polymer's physical, chemical, and electrical properties, and this effect has been widely harnessed in covalently connected MOF-polymer composites. [134][135][136][137] PEG, polyamide, polyurethane, polythiourea, and many biopolymers containing heteroatoms have been widely utilized in composite formation with MOFs to extend their chemical functionalities and tailor their properties for specific applications. In the study of covalent polymerization of polymers bearing heteroatomic backbones on MOFs, the polymerization mechanism is mainly step-growth, unlike polymers with C-C backbones, which follow the chain-growth mechanism.…”