Azodioxides as Inhibitors and Retarders in Photoinitiated Cationic Polymerization. Issue 16 (17th July 2013)

• Record Type: Journal Article
• Authors: Finson, Stephen; Jury, John M.; Crivello, James V.
• Is Part Of: Macromolecular chemistry and physics. Volume 214:Issue 16(2013:Aug.)
• Page Start: 1806
• Page End: 1816
• Publication Date: 2013-07-17
• Subjects: Polymers -- Periodicals; Polymerization -- Periodicals; Synthetic products -- Periodicals; Macromolecules -- Periodicals; 547.7
• DOI: 10.1002/macp.201300300
• Languages: English
• ISSNs: 1022-1352

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>The cyclic azodioxide, 1, 4, 4‐trimethyl‐2, 3‐diazabicyclo[3.2.2]non‐2‐ene 2, 3‐dioxide (<bold>5</bold>), displays the unique ability to function as a thermally reversible inhibitor for the UV‐induced photoinitiated cationic polymerizations of epoxide and vinyl ether monomers. At room temperature and below, the photopolymerizations are suppressed due to the capture of photogenerated initiating protons by the <italic>cis</italic>‐azodioxide group, which is both basic and serves as a bidentate coordinating group. However, at higher temperatures, the azodioxide group reverts to its ring‐opened dinitroso isomer and, as a consequence, loses its ability to coordinate to protons. Protons released during this process subsequently initiate the cationic polymerizations of the monomers. Reversible inhibitors such as <bold>5</bold> have several potential applications such as in the design of one‐component photoactivatable structural and assembly adhesives and in composites. <boxed-text content-type="graphic" position="anchor" orientation="portrait"><graphic position="anchor" mimetype="image" xlink:href="ark:/27927/pgg37f4tb38" orientation="portrait" xlink:type="simple" xmlns:xlink="http://www.w3.org/1999/xlink" /></boxed-text></p> </abstract>