Abstract: In one aspect, methods of depolymerization are described herein comprising providing a synthetic polymer including a hydroxylated aliphatic backbone or hydroxylated backbone segments, and homolytically activing O—H bonds of the hydroxyl groups. Homolytic activation induces the formation of alkoxy radical intermediates followed by C—C bond ?-scission events breaking the polymer backbone into depolymerization products. In some embodiments, depolymerization products comprise alkyl radical intermediates reduced by hydrogen atom transfer. Moreover, in some embodiments, the depolymerization products are further reacted into difunctionalized products or comprise functionalities derived from the polymer structure. The difunctionalized products can subsequently be employed in polymerization processes for the production of additional synthetic polymers.