Azodioxides as Inhibitors and Retarders in Photoinitiated Cationic Polymerization

被引:5
|
作者
Finson, Stephen [1 ]
Jury, John M. [1 ]
Crivello, James V. [2 ]
机构
[1] Hampford Res Inc, Stratford, CT 06615 USA
[2] Rensselaer Polytech Inst, Dept Chem & Chem Biol, New York Ctr Polymer Synth, Troy, NY 12180 USA
关键词
cationic polymerization; crosslinking; irradiation; photopolymerization; ring-opening polymerization; SOLID-STATE; EQUILIBRIA;
D O I
10.1002/macp.201300300
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
The cyclic azodioxide, 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene 2,3-dioxide (5), 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 cis-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 5 have several potential applications such as in the design of one-component photoactivatable structural and assembly adhesives and in composites.
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页码:1806 / 1816
页数:11
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