Formal aryne/ethylene copolymerization to form polyethylene containing o-arylene units in the main chain

• Published in: Polymer journal Vol. 47; no. 7; pp. 474 - 480
• Main Authors: Ito, Shingo, Wang, Wenhan, Nozaki, Kyoko
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 01.07.2015; Nature Publishing Group
• Subjects: 140/131; 639/638/455/941; Addition polymerization; Aliphatic compounds; Alkenes; Biomaterials; Bioorganic Chemistry; Chains (polymeric); Chemistry; Chemistry and Materials Science; Chemistry/Food Science; Copolymerization; Copolymers; Dehydration; Equivalence; Ethylene; Ligands; Organic chemistry; original-article; Palladium; Phosphines; Polyethylenes; Polymer chemistry; Polymer Sciences; Polymerization; Surfaces and Interfaces; Thin Films
• ISSN: 0032-3896; 1349-0540
• DOI: 10.1038/pj.2015.27

As chain-growth polymerization generally forms aliphatic main chains containing units such as alkylene and alkenylene, the method has rarely been applied to the construction of arylene units. Thus, the formation/introduction of arylene groups via chain-growth polymerization remains a challenging subject in polymer chemistry. In this study, we report a formal aryne/ethylene copolymerization using [2.2.1]oxabicyclic alkenes as aryne equivalents. A palladium-catalyzed copolymerization of [2.2.1]oxabicyclic alkenes with ethylene followed by acid-promoted dehydration produced novel aryne/ethylene copolymers. The use of a bulky phosphine–sulfonate ligand was essential to obtain the desired copolymers with high molecular weight. We report a formal aryne/ethylene copolymerization using [2.2.1]oxabicyclic alkenes as aryne equivalents. A palladium-catalyzed copolymerization of [2.2.1]oxabicyclic alkenes with ethylene followed by acid-promoted dehydration produced novel aryne/ethylene copolymers. The use of a bulky phosphine–sulfonate ligand was essential to obtain the desired copolymers with high molecular weight. The present study provides a useful method for the introduction of o -arylene units into the main chains of polyethylene.