Thiol-triggered deconstruction of bifunctional silyl ether terpolymers via an S N Ar-triggered cascade.

Autor: Brown CM; Department of Chemistry, Massachusetts Institute of Technology 77 Massachusetts Avenue Cambridge MA 02139 USA jaj2109@mit.edu., Husted KEL; Department of Chemistry, Massachusetts Institute of Technology 77 Massachusetts Avenue Cambridge MA 02139 USA jaj2109@mit.edu., Wang Y; Department of Chemistry, Massachusetts Institute of Technology 77 Massachusetts Avenue Cambridge MA 02139 USA jaj2109@mit.edu., Kilgallon LJ; Department of Chemistry, Massachusetts Institute of Technology 77 Massachusetts Avenue Cambridge MA 02139 USA jaj2109@mit.edu., Shieh P; Department of Chemistry, Massachusetts Institute of Technology 77 Massachusetts Avenue Cambridge MA 02139 USA jaj2109@mit.edu., Zafar H; Department of Chemistry, Massachusetts Institute of Technology 77 Massachusetts Avenue Cambridge MA 02139 USA jaj2109@mit.edu., Lundberg DJ; Department of Chemistry, Massachusetts Institute of Technology 77 Massachusetts Avenue Cambridge MA 02139 USA jaj2109@mit.edu.; Department of Chemical Engineering, Massachusetts Institute of Technology 77 Massachusetts Avenue Cambridge MA 02139 USA., Johnson JA; Department of Chemistry, Massachusetts Institute of Technology 77 Massachusetts Avenue Cambridge MA 02139 USA jaj2109@mit.edu.; David H. Koch Institute for Integrative Cancer Research, Massachusetts Institute of Technology 77 Massachusetts Avenue Cambridge Massachusetts 02139 USA.
Jazyk: angličtina
Zdroj: Chemical science [Chem Sci] 2023 Aug 02; Vol. 14 (33), pp. 8869-8877. Date of Electronic Publication: 2023 Aug 02 (Print Publication: 2023).
DOI: 10.1039/d3sc02868b
Abstrakt: While Si-containing polymers can often be deconstructed using chemical triggers such as fluoride, acids, and bases, they are resistant to cleavage by mild reagents such as biological nucleophiles, thus limiting their end-of-life options and potential environmental degradability. Here, using ring-opening metathesis polymerization, we synthesize terpolymers of (1) a "functional" monomer ( e.g. , a polyethylene glycol macromonomer or dicyclopentadiene); (2) a monomer containing an electrophilic pentafluorophenyl (PFP) substituent; and (3) a cleavable monomer based on a bifunctional silyl ether . Exposing these polymers to thiols under basic conditions triggers a cascade of nucleophilic aromatic substitution (S N Ar) at the PFP groups, which liberates fluoride ions, followed by cleavage of the backbone Si-O bonds, inducing polymer backbone deconstruction. This method is shown to be effective for deconstruction of polyethylene glycol (PEG) based graft terpolymers in organic or aqueous conditions as well as polydicyclopentadiene (pDCPD) thermosets, significantly expanding upon the versatility of bifunctional silyl ether based functional polymers.
Competing Interests: CMB, PS and JAJ are named inventors on a patent application (US provisional application no. 63/195259) filed by the Massachusetts Institute of Technology on the monomers and copolymers in this work.
(This journal is © The Royal Society of Chemistry.)
Databáze: MEDLINE
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