Addressing the growing demand for sustainable and recyclable polymeric materials requires innovative strategies that combine synthetic accessibility with controlled degradability. This thesis presents three approaches to introduce chemically and thermally labile bonds into radical polymer systems, enabling backbone degradability.

It was first demonstrated that radical homopolymerization of dibenzo[c,e]oxepin-5(7H)-thione (DOT) is inherently inefficient, proceeding only at low conversion. This limitation was overcome through the incorporation of small amounts of diethyl vinylphosphonate (DEVP), where single-unit comonomer insertion generated a secondary radical capable of efficiently initiating DOT propagation. Near-quantitative DOT conversion was achieved with minimal DEVP incorporation, yielding predominantly polythioester structures that underwent complete degradation via aminolysis and thermal treatment.

This work also presents a disulfide-based strategy for embedding degradable units directly into vinyl polymer backbones. Five-membered cyclic disulfide (1,2-dithiolane) was synthesized in high purity and successfully copolymerized with various vinyl monomers under radical conditions. The resulting copolymers incorporated backbone disulfide linkages that enabled efficient reductive chain scission. This concept was further applied to recyclable coatings using both solution-based and solvent-free thermal processing, producing uniform coatings that can be removed by heating.

The introduction of thioester units was subsequently extended to crosslinked styrene and dimethyl acrylamide based networks. These materials maintained their thermomechanical properties before cleavage but underwent full degradation under mild conditions. The resulting fragments enabled re-gelation and were further upcycled into mixed gel networks containing both hydrophilic and hydrophobic components, restoring crosslink density and mechanical integrity.