Facile synthesis of monocyclic, dumbbell-shaped and jellyfish-like copolymers using a telechelic multisite hexablock copolymer

The combination of cyclic and comblike blocks in architectural polymers can provide insight into topology-dependent physical properties. Despite tremendous progress, jellyfish-like polymers (JFPs) with a macrocycle-bearing backbone have been scarcely reported. To enrich the family of JFPs, a teleche...

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Bibliographic Details
Published in:Polymer chemistry 2022-08, Vol.13 (34), p.4953-4965
Main Authors: Zhu, Yingsheng, Liu, Peng, Zhang, Jian, Hu, Jiaman, Zhao, Youliang
Format: Article
Language:English
Subjects:
Bromine
Chemical reactions
Chemical synthesis
Copolymers
Folding
Graft copolymers
Physical properties
Polyacrylic acid
Polyethylene glycol
Polymer chemistry
Polymers
Polystyrene resins
Self-assembly
Topology
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Summary:The combination of cyclic and comblike blocks in architectural polymers can provide insight into topology-dependent physical properties. Despite tremendous progress, jellyfish-like polymers (JFPs) with a macrocycle-bearing backbone have been scarcely reported. To enrich the family of JFPs, a telechelic multisite hexablock copolymer comprising alternating sequences of poly(styrene- co -maleimide) and polystyrene blocks and diverse functionalities of thiolactone, hydroxyl and bromine is designed. The first intrachain folding affords a cyclic copolymer, followed by the second intracyclic folding via a thio-bromo click reaction to achieve a dumbbell-shaped copolymer. The subsequent graft reactions and hydrolysis afford homografted and heterografted JFPs comprising poly( -caprolactone), poly(ethylene glycol), poly( tert -butyl acrylate) and/or poly(acrylic acid) segments. Depending on the topology, composition and solution pH, distinct nano-objects including spheres, vesicles, cylinders, spindles and lamellae are fabricated by self-assembly. Rational design of multisite multiblock copolymers holds great promise in the construction of novel JFPs comprising macrocycle- and folding block-bearing backbones. A heterofunctional hexablock copolymer comprising alternating reactive and non-reactive blocks is designed to generate cyclic, dumbbell-shaped and jellyfish-like copolymers.
ISSN:1759-9954
1759-9962
DOI:10.1039/d2py00824f