A Readily Scalable Silylated Cyclic Allyl Sulfide Monomer for Degradable Vinyl Polymers
6 affiliations
- 1Aix-Marseille University CNRS, Institut de Chimie Radicalaire, UMR
- 2Université de Haute-Alsace, CNRS, IS2M UMR
- 3CNRS
- 4Institut Galien Paris-Saclay
- 5COATEX SAS
- 6ARKEMA, CERDATO
Abstract
Introducing degradability into conventional vinyl polymers without sacrificing the versatility of radical polymerization remains a major challenge. Radical Ring-Opening Polymerization (rROP) is currently the most promising technique to impart degradability into vinyl-based polymers through the copolymerization of cyclic monomers with common vinyl monomers. However, among the various families of cyclic monomers reported to date, none simultaneously combines high efficiency, versatility, and compatibility with industrial-scale production. Here, we report a family of silylated cyclic allylic sulfides (CAS) designed to decouple radical ring-opening reactivity from post-polymerization cleavage. The representative monomer LC1 combines a CAS scaffold, which undergoes efficient radical addition–fragmentation, with an independently cleavable silyl ether linkage. LC1 is prepared in two steps from readily available precursors, and a simultaneous dual-feed strategy enables its facile and reproducible scale-up. LC1 displays monomer-dependent reactivity across several vinyl monomer families and introduces cleavable junctions throughout chain growth. Kinetic experiments, Mayo analysis and density functional theory reveal two distinct addition–fragmentation processes: rapid ring-opening incorporation of cyclic LC1 followed by a slower secondary transfer pathway involving the pendant allylic functionality generated after ring opening. The resulting polymers undergo backbone fragmentation under fluoride, acidic, basic and Lewis-acid conditions, with degradation kinetics further tunable through pH and silicon substitution. LC1 also remains compatible with emulsion polymerization and crosslinked networks, enabling chemically and thermally triggered disassembly of 3D-printed materials. Finally, in the context of upcycling, hydroxyl-terminated degradation fragments can be repurposed as polyol precursors for polyurethane network formation. This work establishes silylated CAS monomers as a versatile platform for independently programming radical polymer growth and material lifetime.
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BibTeX
@misc{choulot2026readily,
title = {{A Readily Scalable Silylated Cyclic Allyl Sulfide Monomer for Degradable Vinyl Polymers}},
author = {Luna Choulot and Sophia Kouider and Maxime Ria and Hassiba Boutarfa and Loic Buchon and Teodora Tomovic and Didier Gigmes and Didier Siri and Julien Nicolas and Laurence Charles and Olivier Soppera and Catherine Lefay and Guillaume Michaud and Jean-Jacques Flat and Yohann Guillaneuf},
howpublished = {ChemRxiv},
year = {2026},
month = oct,
doi = {10.26434/chemrxiv.15010975/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010975/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - A Readily Scalable Silylated Cyclic Allyl Sulfide Monomer for Degradable Vinyl Polymers
AU - Luna Choulot
AU - Sophia Kouider
AU - Maxime Ria
AU - Hassiba Boutarfa
AU - Loic Buchon
AU - Teodora Tomovic
AU - Didier Gigmes
AU - Didier Siri
AU - Julien Nicolas
AU - Laurence Charles
AU - Olivier Soppera
AU - Catherine Lefay
AU - Guillaume Michaud
AU - Jean-Jacques Flat
AU - Yohann Guillaneuf
PY - 2026
DA - 2026/10/23
PB - ChemRxiv
DO - 10.26434/chemrxiv.15010975/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010975/v1
AB - Introducing degradability into conventional vinyl polymers without sacrificing the versatility of radical polymerization remains a major challenge. Radical Ring-Opening Polymerization (rROP) is currently the most promising technique to impart degradability into vinyl-based polymers through the copolymerization of cyclic monomers with common vinyl monomers. However, among the various families of cyclic monomers reported to date, none simultaneously combines high efficiency, versatility, and compatibility with industrial-scale production. Here, we report a family of silylated cyclic allylic sulfides (CAS) designed to decouple radical ring-opening reactivity from post-polymerization cleavage. The representative monomer LC1 combines a CAS scaffold, which undergoes efficient radical addition–fragmentation, with an independently cleavable silyl ether linkage. LC1 is prepared in two steps from readily available precursors, and a simultaneous dual-feed strategy enables its facile and reproducible scale-up. LC1 displays monomer-dependent reactivity across several vinyl monomer families and introduces cleavable junctions throughout chain growth. Kinetic experiments, Mayo analysis and density functional theory reveal two distinct addition–fragmentation processes: rapid ring-opening incorporation of cyclic LC1 followed by a slower secondary transfer pathway involving the pendant allylic functionality generated after ring opening. The resulting polymers undergo backbone fragmentation under fluoride, acidic, basic and Lewis-acid conditions, with degradation kinetics further tunable through pH and silicon substitution. LC1 also remains compatible with emulsion polymerization and crosslinked networks, enabling chemically and thermally triggered disassembly of 3D-printed materials. Finally, in the context of upcycling, hydroxyl-terminated degradation fragments can be repurposed as polyol precursors for polyurethane network formation. This work establishes silylated CAS monomers as a versatile platform for independently programming radical polymer growth and material lifetime.
ER -