Stereospecific Anionic Polymerization of α‐(Hydroxymethyl)acrylate with Protective Group. Issue 1 (April 2015)

• Record Type: Journal Article
• Authors: Kohsaka, Yasuhiro; Suzawa, Kazuha; Kitayama, Tatsuki; Kitayama, Tatsuki; Aoshima, Sadahito; Kamigaito, Masami
• Is Part Of: Macromolecular symposia. Volume 350:Issue 1(2015)
• Page Start: 86
• Page End: 98
• Publication Date: 2015-04
• Subjects: Macromolecules -- Congresses; Polymers -- Congresses; Polymerization -- Congresses; Macromolecules -- Periodicals; Polymers -- Periodicals; Polymerization -- Periodicals; 547.705
• DOI: 10.1002/masy.201400028
• Languages: English
• ISSNs: 1022-1360

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Summary</title> <sec id="masy201400028-sec-0001" sec-type="section"> <p>Anionic polymerizations of hydroxyl‐protected α‐(hydroxymethyl)acrylates were investigated. The methyl ester with methoxymethyl (<bold>1‐MOM</bold>) and allyl (<bold>1‐allyl</bold>) protecting groups were polymerized by isopropyl α‐lithioisobutyrate (Li‐<italic>i</italic>PrIB) in toluene at −78 °C, affording highly isotactic polymers. Similarly, the polymerization of ethyl ester (<bold>2‐MOM</bold>) gave an isotactic polymer, while those of <italic>t</italic>‐butyl (<bold>3‐MOM</bold>) and isobutyl (<bold>4‐MOM</bold>) ester did not form any polymeric products. The hydrolysis of <bold>poly(2‐MOM)</bold> in acidic conditions resulted in the deprotection of MOM group, although the acid also catalyzed the ester exchange between the neighboring units to form lactone units, as observed by ¹H NMR analysis, IR spectroscopy and thermogravimetric analysis. A film of <bold>poly(2‐MOM)</bold> exposed to HCl vapor for 2 h became insoluble in any organic solvents due to the lactonization in solid state.</p> </sec> </abstract>