Metal-ions directed self-assembly of hybrid diblock copolymers
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Metal-ions directed self-assembly of hybrid diblock copolymers Birong Zeng,a) Yueguang Wu, Qilong Kang, Ying Chang, Conghui Yuan, and Yiting Xu Department of Material Science and Engineering, Fujian Provincial Key Laboratory of Fire Retardant Materials, College of Materials, Xiamen University, Xiamen Fujian 361005, People’s Republic of China
Feng-Chih Chang Department of Materials and Optoelectronic Science, National Sun Yat-Sen University, Kaohsiung 804, Taiwan
Lizong Daib) Department of Material Science and Engineering, Fujian Provincial Key Laboratory of Fire Retardant Materials, College of Materials, Xiamen University, Xiamen Fujian 361005, People’s Republic of China (Received 16 January 2014; accepted 10 September 2014)
Novel hybrid diblock copolymers consisting of bidentate ligand-functionalized chains have been synthesized via click reaction and RAFT radical polymerization. The chemical structure and molecular weight of the synthesized poly (methacrylate-POSS)-block-poly(4-vinylbenzyl-2-pyridine-1H-1,2,3-triazole) (PMAPOSS-b-PVBPT) were characterized by NMR and GPC. The copolymers had been utilized to construct metal-containing polymer micelle by the metal–ligand coordination and electrostatic interaction in this study. The self-assembly behaviors of PMAPOSS-b-PVBPT in chloroform, a common solvent, under the effect of Zn(OTf)2 and HAuCl 4 were investigated by TEM, DLS, and variable temperature NMR. Besides, micellization of this diblock copolymer was achieved in ethylene glycol, a selective solvent for PMAPOSS-b-PVBPT. The experimental results revealed that the incorporation of heterocyclic rings bearing nitrogen atoms in polymer side chains played an important role in the construction of metal-containing copolymer micelles. The prepared metal-containing PMAPOSS-b-PVBPT micelles had good dynamic and thermal stability due to the strong metal–ligand coordination interaction and electrostatic interaction.
I. INTRODUCTION
Address all correspondence to these authors. a) e-mail: [email protected] b) e-mail: [email protected] DOI: 10.1557/jmr.2014.292
(POSS) with an inorganic cage (SiO1.5)n structure surrounded by eight organic groups has many advantages of being nontoxic, biocompatible, and mechanically stable, and so on.16–19 Due to its special structure and chemical characteristics, POSS-containing copolymers have become one of the interesting areas in the field of organic– inorganic hybrid materials and attracted more and more attentions in the past decades.20–24 In our present work, we developed a novel block copolymer consisting of hybrid POSS units and pyridine-1,2,3-triazole groups for the formation of metalcontaining polymer micelles. It is expected that the selfassembly of the designed diblock copolymer can be induced by supramolecular interactions including hydrophobic interaction and metal–ligand coordination as well as electrostatic interaction. Firstly, we synthesized the ligand 4-vinylbenzyl-2-pyridine-1H-1,2,3-triazole (VBPT) by using copper-catalyzed click reaction, and then incorporated it int
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