Facile Synthesis of Well‐Defined Branched Sulfur‐Containing Copolymers: One‐Pot Copolymerization of Carbonyl Sulfide and Epoxide

Topological polymers possess many advantages over linear polymers. However, when it comes to the poly(monothiocarbonate)s, no topological polymers have been reported. Described herein is a facile and efficient approach for synthesizing well‐defined branched poly(monothiocarbonate)s in a “grafting th...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2020-08, Vol.59 (32), p.13633-13637
Main Authors: Yue, Tian‐Jun, Bhat, Gulzar A., Zhang, Wen‐Jian, Ren, Wei‐Min, Lu, Xiao‐Bing, Darensbourg, Donald J.
Format: Article
Language:English
Subjects:
Carbonyl compounds
Carbonyl sulfide
Carbonyls
Copolymerization
Copolymers
Epichlorohydrin
epoxides
Graft copolymers
Polymers
structure elucidation
Sulfide
Sulfides
Sulfur
synthetic methods
Thermal properties
Thermodynamic properties
Topology
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Summary:Topological polymers possess many advantages over linear polymers. However, when it comes to the poly(monothiocarbonate)s, no topological polymers have been reported. Described herein is a facile and efficient approach for synthesizing well‐defined branched poly(monothiocarbonate)s in a “grafting through” manner by copolymerizing carbonyl sulfide (COS) with epichlorohydrin (ECH), where the side‐chain forms in situ. The lengths of the side‐chains are tunable based on reaction temperatures. More importantly, enhancement in thermal properties of the branched copolymer was observed, as the Tg value increased by 22 °C, compared to the linear analogues. When chiral ECH was utilized, semicrystalline branched poly(monothiocarbonate)s were accessible with a Tm value of 112 °C, which is 40 °C higher than that of the corresponding linear poly(monothiocarbonate)s. The strategy presented herein for synthesizing branched polymers provides efficient and concise access to topological polymers. Branch out: A novel strategy for the synthesis of branched poly(monothiocarbonate)s is presented. Branched poly(monothiocarbonate)s are synthesized with tunable side‐chain lengths and densities by adjusting the reaction temperature.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202005806