A novel class of enyne self-immolative polymers (SIPs) capable of metathesis cascade-triggered depolymerization is reported. Studies on model compounds established 1,6enyne structures for efficient metathesis cascade reactions. SIPs incorporating the optimized 1,6-enyne motif were prepared via both polycondensation and iterative exponential growth approaches. These SIPs demonstrated excellent stability in strong acid, base, nucleophiles, or at elevated temperatures, and can undergo efficient and complete depolymerization once triggered by a metathesis catalyst. Further studies revealed that introducing a terminal alkene to the chain end of the enyne SIPs improved the depolymerization efficiency, and established their potential as stimuli-responsive materials. Scheme 1. Development of the enyne self-immolative polymer. Scheme 2. Enyne metathesis of model compounds.

As an inedible component of biomass, lignin features rich functional groups that are desired for chemical syntheses. How to effectively depolymerize lignin without compromising the more valuable cellulose and hemicellulose has been a significant challenge. Existing biomass processing procedures either induce extensive condensation in lignin that greatly hinders its chemical utilization or focus on fully depolymerizing lignin to produce monomers that are difficult to separate for subsequent chemical synthesis. Here, we report a new approach to selective partial depolymerization, which produces oligomers that can be readily converted to chemically recyclable polymer networks. The process takes advantage of the high selectivity of photocatalytic activation of the β-O-4 bond in lignin by tetrabutylammonium decatungstate (TBADT). The availability of exogenous electron mediators or scavengers promotes cleavage or oxidation of this bond, respectively, enabling high degrees of control over the depolymerization and the density of a key functional group, C�O, in the products. The resulting oligomers can then be readily utilized for the synthesis of polymer networks through reactions between C�O and branched −NH 2 as a dynamic covalent cross-linker. Importantly, the resulting polymer network can be recycled to enable a circular economy of materials directly derived from biomass.

A novel class of enyne self-immolative polymers (SIPs) capable of metathesis cascade-triggered depolymerization is reported. Studies on model compounds established 1,6enyne structures for efficient metathesis cascade reactions. SIPs incorporating the optimized 1,6-enyne motif were prepared via both polycondensation and iterative exponential growth approaches. These SIPs demonstrated excellent stability in strong acid, base, nucleophiles, or at elevated temperatures, and can undergo efficient and complete depolymerization once triggered by a metathesis catalyst. Further studies revealed that introducing a terminal alkene to the chain end of the enyne SIPs improved the depolymerization efficiency, and established their potential as stimuli-responsive materials. Scheme 1. Development of the enyne self-immolative polymer. Scheme 2. Enyne metathesis of model compounds.

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A novel class of enyne self-immolative polymers (SIPs) capable of me-tathesis cascade-triggered depolymerization is reported. Studies on mod-el compounds established 1,6-enyne structures for efficient metathesis cascade reactions. SIPs incorporating the optimized 1,6-enyne motif were prepared via both polycondensation and iterative exponential growth ap-proaches. These SIPs demonstrated excellent stability in strong acid, base, and nucleophiles, and can undergo efficient and complete depoly-merization once triggered by a metathesis catalyst. Further studies re-vealed that introducing a terminal alkene to the chain end of the enyne SIPs improved the depolymerization efficiency, and established their potential as stimuli-responsive materials.