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Living Ring-Opening Polymerization of Cyclic Esters with Epoxide-Derived Titanium Alkoxides

✍ Scribed by Alexandru D. Asandei; Gobinda Saha

Publisher
John Wiley and Sons
Year
2005
Tongue
English
Weight
144 KB
Volume
26
Category
Article
ISSN
1022-1336

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✦ Synopsis

Abstract

Summary: The Ti^III^Cp~2~Cl‐catalyzed radical ring opening of epoxides produces Ti alkoxides which initiate the ring‐opening polymerization of ε‐caprolactone. A linear dependence of $\overline M _{\rm n}$ on conversion, linear kinetics, low $\overline M _{\rm w} /\overline M _{\rm n}$ values, and the synthesis of block copolymers demonstrate a living process, while NMR spectroscopy confirms the presence of the initiator chain end. Epoxides are thus introduced as a new class of initiators for the Ti‐catalyzed living ring‐opening polymerization of cyclic esters.

The TiCp~2~Cl‐catalyzed radical ring opening of epoxides followed by the initiation of the living ring‐opening polymerization of ε‐caprolactone.

magnified imageThe TiCp~2~Cl‐catalyzed radical ring opening of epoxides followed by the initiation of the living ring‐opening polymerization of ε‐caprolactone.

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A density functional theory study of the
A density functional theory study of the mechanisms of scandium-alkoxide initiated coordination–insertion ring-opening polymerization of cyclic esters
✍ Jun Ling; Jingguo Shen; Thieo E. Hogen-Esch 📂 Article 📅 2009 🏛 Elsevier Science 🌐 English ⚖ 346 KB

The generally accepted coordination-insertion mechanisms of scandium-alkoxide initiated ring-opening polymerizations of 3-caprolactone (CL), trimethylene carbonate (TMC) and (S,S)-lactide (LLA) were investigated using density functional theory calculations. The geometries and corresponding energies