Aldol‐type group‐transfer polymerization of silyl vinyl ethers using silyl perfluoroalkaneimides as nonmetal catalysts. Issue 16 (29th May 2013)

• Record Type: Journal Article
• Authors: Moyori, Takaya; Hayashi, Terunari; Takasu, Akinori
• Is Part Of: Journal of polymer science. Volume 51:Issue 16(2013:Aug.)
• Page Start: 3516
• Page End: 3522
• Publication Date: 2013-05-29
• Subjects: 547
• DOI: 10.1002/pola.26753
• Languages: English
• ISSNs: 0887-624X

Abstract

<abstract abstract-type="main"> <title>ABSTRACT</title> <p>We investigated the catalytic activity of bis(nonafluorobutanesulfonyl)imide (Nf<sub>2</sub>NH), acting as a Brønsted acid, and its silylated imide, <italic>t</italic>‐butyldimethylsilyl nonafluorobutanesulfonylimide (Nf<sub>2</sub>NTBDMS), acting as a Lewis acid, for aldol‐type of group‐transfer polymerization (Aldol‐GTP) of silyl vinyl ethers. Aldol‐GTPs of <italic>t</italic>‐butyldimethylsilyl vinyl ether (VOTBDMS) and triethylsilyl vinyl ether (VOTES) proceeded in dichloromethane at 0 °C with benzaldehyde as the initiator. Nf<sub>2</sub>NH catalyzed the polymerization of VOTBDMS although the product poly(VOTBDMS) had a molecular weight of 2510, which was considerably smaller than that predicted by the ratio of the initial monomer to initiator concentrations, and the smaller molecular weight was a consequence of desilylation of VOTBDMS before the polymerization step. Conversely, when Nf<sub>2</sub>NTBDMS was used as the catalyst, poly(VOTBDMS) with molecular weight >16, 000 was obtained. The Nf<sub>2</sub>NTBDMS‐catalyzed polymerization was more rapid than polymerizations that used <italic>t</italic>‐butyldimethylsilyl trifluoromethanesulfonylimide, <italic>t</italic>‐butyldimethylsilyl hexafluorocycropropanesulfonylimide, or zinc bromide as the catalyst, even though the ratio of Nf<sub>2</sub>NTBDMS to the monomer was the smallest used. With VOTES as the monomer, and Tf<sub>2</sub>NTBDMS as the catalyst, a poly(VOTES) with a syndiotactic tendency (mm:mr:rr = 9:44:47) was produced. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. <bold>2013</bold>, <italic>51</italic>, 3516–3522</p> </abstract>