mz9b00463_si_001.pdf (3.82 MB)
Synthesis of Rapidly Surface Eroding Polyorthoesters and Polyacetals Using Thiol–ene Click Chemistry
journal contribution
posted on 2019-09-17, 11:33 authored by Gordon Herwig, Andrew P. DovePolyorthoesters are generally considered
to be highly biocompatible,
surface-eroding materials. However, sensitive intermediates and poor
mechanical performance have largely prevented their widespread application
to date. Herein, a simple and versatile method to synthesize orthoester-
and acetal-based polymers is presented. Using 2-methylene-1,3-dioxe-5-pene
as a stable bifunctional monomer, sequential highly selective “click”
reactions led initially to the formation of orthoesters (OE) in a
Markovnikov alcohol addition or acetals via anti-Markovnikov thiol–ene
addition. Subsequent photoinitiated thiol addition onto the remaining
endocyclic and backbone alkene functionalities lead to thioether formation
to produce a class of poly(orthoester-thioether)s or poly(acetal-thioether)s
via a step-growth polymerization. While all obtained polymers were
found to possess a weight-average molecular weight of above 10 kg·mol–1, the application of an OE monomer with additional
double bond functionality led to a cross-linked polymer network which
displayed surface-erosion behavior.
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surface-eroding materialsRapidly Surface Eroding Polyorthoestersacetal-based polymerscross-linked polymer networksurface-erosion behaviorbackbone alkene functionalitiesbifunctional monomerapplicationSubsequent photoinitiated thiol additionthioether formationOE monomerbond functionalityMarkovnikov alcohol additionstep-growth polymerization
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