Bio-based cinnamoyl-functional poly(butylene succinate) (PBS) copolyesters were synthesized to investigate the effect of photoinduced structural changes on polymer thermal and mechanical behaviour. The photoactive cinnamoyl amide monomer was prepared through an optimized sustainable synthetic pathway selected by comparative green metrics analysis, including Process Mass Intensity (PMI), Atom Economy (AE), and Molar Efficiency (MolE%). Incorporation of the cinnamoyl units into the PBS backbone afforded copolymers with tunable thermal and mechanical properties that underwent significant modifications upon UV and solar irradiation. Although cinnamoyl derivatives are widely used as photoactive motifs, their solid-state photochemistry is often ambiguously interpreted due to the coexistence of configurational isomerization and [2 + 2] photocycloaddition pathways. Here, quantitative NMR spectroscopy was employed to distinguish and quantify these competing processes in the solid state, revealing that photoisomerization predominates under the investigated conditions, while photocrosslinking remains limited. Correlation of structural evolution with thermal and mechanical analyses indicates that cinnamoyl pendants modulate chain organization and crystallization behaviour in PBS-based copolyesters. These findings provide mechanistic insight into the solid-state photochemistry of cinnamoyl-functional polymers and establish a sustainable platform for the development of light-responsive polymeric materials.
Bio-based cinnamoyl-functional poly(butylene succinate) copolyesters: photoisomerization behaviour and structure–property relationships
Lambruschini C.;Guidotti G.;Banfi L.;Pellis A.;Riva R.;Lotti N.;Moni L.
2026-01-01
Abstract
Bio-based cinnamoyl-functional poly(butylene succinate) (PBS) copolyesters were synthesized to investigate the effect of photoinduced structural changes on polymer thermal and mechanical behaviour. The photoactive cinnamoyl amide monomer was prepared through an optimized sustainable synthetic pathway selected by comparative green metrics analysis, including Process Mass Intensity (PMI), Atom Economy (AE), and Molar Efficiency (MolE%). Incorporation of the cinnamoyl units into the PBS backbone afforded copolymers with tunable thermal and mechanical properties that underwent significant modifications upon UV and solar irradiation. Although cinnamoyl derivatives are widely used as photoactive motifs, their solid-state photochemistry is often ambiguously interpreted due to the coexistence of configurational isomerization and [2 + 2] photocycloaddition pathways. Here, quantitative NMR spectroscopy was employed to distinguish and quantify these competing processes in the solid state, revealing that photoisomerization predominates under the investigated conditions, while photocrosslinking remains limited. Correlation of structural evolution with thermal and mechanical analyses indicates that cinnamoyl pendants modulate chain organization and crystallization behaviour in PBS-based copolyesters. These findings provide mechanistic insight into the solid-state photochemistry of cinnamoyl-functional polymers and establish a sustainable platform for the development of light-responsive polymeric materials.
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