Controlled and Regioselective Ring-Opening Polymerization for Poly(disulfide)s by Anion-Binding Catalysis DOI Creative Commons

Tianyi Du,

Boming Shen,

Jieyu Dai

et al.

Published: Oct. 25, 2023

Poly(disulfide)s are an emerging class of sulfur-containing polymers with applications in medicine, energy, and functional materials. However, the constituent dynamic covalent S−S bond is highly reactive presence sulfide (RS−) anion, imposing a persistent challenge to control polymerization. Here, we report anion-binding approach arrest high reactivity RS− chain end synthesis linear poly(disulfide)s, realizing rapid, living ring-opening polymerization 1,2-dithiolanes narrow dispersity regioregularity (Mw /Mn ~ 1.1, Ps 0.85). Mechanistic studies support formation thiourea-base-sulfide ternary complex as catalytically active species during propagation. Theoretical analyses reveal synergistic catalytic model where catalyst preorganizes protonated base anionic establish spatial confinement over bound monomer, effecting observed regioselectivity. The system amenable monomers various groups, semicrystalline also obtained from lipoic acid derivatives by enhancing regioregularity.

Language: Английский

Controlled and Regioselective Ring-Opening Polymerization for Poly(disulfide)s by Anion-Binding Catalysis DOI Creative Commons

Tianyi Du,

Boming Shen,

Jieyu Dai

et al.

Published: Oct. 25, 2023

Poly(disulfide)s are an emerging class of sulfur-containing polymers with applications in medicine, energy, and functional materials. However, the constituent dynamic covalent S−S bond is highly reactive presence sulfide (RS−) anion, imposing a persistent challenge to control polymerization. Here, we report anion-binding approach arrest high reactivity RS− chain end synthesis linear poly(disulfide)s, realizing rapid, living ring-opening polymerization 1,2-dithiolanes narrow dispersity regioregularity (Mw /Mn ~ 1.1, Ps 0.85). Mechanistic studies support formation thiourea-base-sulfide ternary complex as catalytically active species during propagation. Theoretical analyses reveal synergistic catalytic model where catalyst preorganizes protonated base anionic establish spatial confinement over bound monomer, effecting observed regioselectivity. The system amenable monomers various groups, semicrystalline also obtained from lipoic acid derivatives by enhancing regioregularity.

Language: Английский

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