Facile synthesis of calabash-shaped and twin-tail tadpole-shaped copolymers via photothermal-induced topological transformation
Zhigang Wang,
Yong Lin,
Youliang Zhao
Affiliations
Zhigang Wang
Suzhou Key Laboratory of Macromolecular Design and Precision Synthesis, Key Laboratory of Polymeric Materials Design and Synthesis for Biomedical Function, Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application, State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, China
Yong Lin
Suzhou Key Laboratory of Macromolecular Design and Precision Synthesis, Key Laboratory of Polymeric Materials Design and Synthesis for Biomedical Function, Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application, State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, China
Youliang Zhao
Corresponding author.; Suzhou Key Laboratory of Macromolecular Design and Precision Synthesis, Key Laboratory of Polymeric Materials Design and Synthesis for Biomedical Function, Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application, State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, China
Rational design of architecture-transformable polymers with dynamic covalent bonds allows to form multiple ring-bearing analogues and gain insight into topology-tunable physicochemical properties. To reveal unique properties originating from size-asymmetric twincycles and ring-linear conjugates, twin-tail tadpole-shaped (TTP) and calabash-shaped bicyclic (CLB) copolymers comprising poly(ε-caprolactone) (PCL, A) and polystyrene (PSt, B) segments are synthesized. Controlled polymerization and radical trap-assisted atom transfer radical coupling are combined to synthesize a multisite telechelic ABA. By virtue of UV-induced intramolecular anthracene dimerization and selective thermolysis of in-chain alkoxyamine and anthracene dimer linkers of the macrocycle, versatile topological transformations from linear copolymer to TTP, CLB and ring/tail-reversal TTP are achieved. Owing to distinct chain architectures, three types of analogues can exhibit some differences in hydrodynamic volume, crystallization, diffusion coefficient and aggregation behavior, revealing pronounced topology effect. This study affords a promising method to construct stimuli-labile ring-bearing architectures to reveal topology-dependent properties.
