Redox initiated cationic polymerization of oxetanes. Issue 16 (14th May 2015)

• Record Type: Journal Article
• Authors: Crivello, James V.
• Is Part Of: Journal of polymer science. Volume 53:Issue 16(2015:Aug.)
• Page Start: 1854
• Page End: 1861
• Publication Date: 2015-05-14
• Subjects: 547
• DOI: 10.1002/pola.27553
• Languages: English
• ISSNs: 0887-624X

Abstract

<abstract abstract-type="main"> <title>ABSTRACT</title> <p>3, 3‐Disubstituted oxetane monomers were found to undergo rapid, exothermic redox initiated cationic ring‐opening polymerization in the presence of a diaryliodonium or triarylsulfonium salt oxidizing agent and a hydrosilane reducing agent. The redox reaction requires a noble metal complex as a catalyst and several potential catalysts were evaluated. The palladium complex, Cl₂(COD)Pd^II, was observed to provide good shelf life stability while, at the same time, affording high reactivity in the presence of a variety of hydrosilane reducing agents. A range of structurally diverse oxetane monomers undergo polymerization under redox cationic conditions. When a small amount of an alkylated epoxide was added as a "kick‐start" accelerator to these same oxetanes, the redox initiated cationic polymerizations were extraordinarily rapid owing to the marked reduction in the induction period. A mechanistic interpretation of these results is offered. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. <bold>2015</bold>, <italic>53</italic>, 1854–1861</p> </abstract>