Linear and Network-Forming Acetal Polymerization of Multifunctional Alcohols with Dichloromethane for Degradable and Recyclable Materials

Although thermoplastic and thermoset materials have revolutionized modern living, their widespread use has also led to significant environmental challenges due to limited recyclability and persistence in the environment. To address these issues, the development of new materials that are both functional and sustainable is crucial. In this work, an acetal-based polymerization is demonstrated, wherein dichloromethane (DCM) serves as a methylene synthon for forming acetals between alcohol end groups in the presence of a strong base, facilitating the production of fully degradable polymers and networks, as well as facile recovery of repolymerizable monomers. The incorporation of functional groups via primary alcohols, such as norbornene methanol, enables simultaneous functionalization of the polymer structure. Glycol-based linear polymers and macromers are utilized as primary building blocks, offering a versatile platform for generating tunable polymer architectures. Additionally, acetal-based oligomerization of decanediol is achieved at increased temperature and pressure, broadening the scope of potential materials accessible through this method. This historically understudied reaction holds great promise for the design of functional, degradable, and recyclable polymers.