An Efficient and General Strategy toward the Synthesis of Polyethylene-Based Cyclic Polymers

• Published in: Macromolecules Vol. 51; no. 8; pp. 3193 - 3202
• Main Authors: Jiang, Yu, Zhang, Zhen, Wang, De, Hadjichristidis, Nikos
• Format: Journal Article
• Language: English
• Published: American Chemical Society 24.04.2018
• Subjects: anthracenes; composite polymers; crystal structure; cycloaddition reactions; differential scanning calorimetry; esterification; gel chromatography; melting point; moieties; nuclear magnetic resonance spectroscopy; polyethylene; polymerization; tadpoles; thermal properties
• DOI: 10.1021/acs.macromol.8b00333
• ISSN: 0024-9297; 1520-5835

A novel strategy toward well-defined polyethylene-based cyclic homo/copolymers is presented. Tris­(3-(anthracen-9-yl­methoxy)­propyl)­borane, prepared by hydroboration of 9-((allyloxy)­methyl)­anthracene with BH3, was used to initiate the polyhomologation of dimethyl­sulfoxonium methylide to afford well-defined anthracene-teminated linear polyethylene (PE). The azido and alkynyl groups at α and ω positions of the PE chain were introduced via the anthracene/maleimide Diels–Alder (D–A) reaction and esterification, respectively. Subsequent intramolecular “click” cyclization of the α,ω-hetero­functionalized linear PE gave cyclic PE. Combining this efficient strategy with ring-opening polymerization (ROP), more complex PE-based cyclic block copolymer architectures have been designed and synthesized, such as diblock cyclic and triblock tadpole copolymers. All intermediates and final products were characterized by high-temperature gel permeation chromatography, proton nuclear magnetic resonance spectroscopy, and differential scanning calorimetry. Initial studies on the thermal behavior of the cyclic homo- and block copolymers revealed the big influence of the cyclic structure on the melting temperature and crystallinity as compared to their corresponding precursors.