Entropy-Driven Ring-Opening Disulfide Metathesis Polymerization for the Synthesis of Functional Poly(disulfide)s

Felix N Behrendt; Helmut Schlaad

doi:10.1002/marc.201700735

Entropy-Driven Ring-Opening Disulfide Metathesis Polymerization for the Synthesis of Functional Poly(disulfide)s

Macromol Rapid Commun. 2018 Mar;39(6):e1700735. doi: 10.1002/marc.201700735. Epub 2018 Jan 5.

Authors

Felix N Behrendt¹, Helmut Schlaad¹

Affiliation

¹ Institute of Chemistry, University of Potsdam, Karl-Liebknecht-Straße 24-25, 14476, Potsdam, Germany.

PMID: 29315953
DOI: 10.1002/marc.201700735

Abstract

Metal-free entropy-driven disulfide metathesis polymerization of unsaturated l-cystine based macrocycles produces high-molar-mass heterofunctional poly(disulfide)s, i.e., poly(ester-disulfide-alkene) and poly(amide-disulfide-alkene); M_w^app = 44-60 kDa, Ð > 1.7. The polymerization is fast and reaches equilibrium within 1-5 minutes (monomer conversion 70-90%) in polar aprotic solvents such as N,N-dimethylacetamide, dimethylsulfoxide, or γ-valerolactone. Thiol-terminated polymers are stable in bulk or when dissolved in weakly polar solvents, but rapidly depolymerize in dilute polar solution.

Keywords: disulfide; macrocycles; metathesis; ring-opening polymerization.

MeSH terms

Disulfides / chemistry*
Entropy*
Molecular Weight
Polymerization
Polymers / chemistry*

Substances

Disulfides
Polymers