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http://dx.doi.org/10.5012/bkcs.2007.28.12.2471

Efficient Bimodal Ring-opening Polymerization of ε-Caprolactone Catalyzed by Titanium Complexes with N-Alkoxy-β-ketoiminate Ligands  

Cho, Min-Ho (Department of Chemistry, Inha University)
Yoon, Jin-San (Department of Polymer Engineering, Inha University)
Lee, Ik-Mo (Department of Polymer Engineering, Inha University)
Publication Information
Bulletin of the Korean Chemical Society / v.28, no.12, 2007 , pp. 2471-2476 More about this Journal
Abstract
A series of titanium complexes containing terdentate β-ketoiminate ligands were found to be efficient for the ring-opening polymerization of ε-caprolactone (ε-CL), producing poly(ε-caprolactone) (PCL) with bimodal distribution. Steric factors imposed by methyl substituents on the back bone of the alkoxy group affected significantly the polymerization rate and physical properties of the resulting PCL. Intra- and intermolecular transesterifications rather than disproportional rearrangements were responsible for the bimodal behavior and for the change in the molecular weight (Mw). Dilution with toluene reduced yield, and lowered polydispersity (PDI) and Mw of PCL, while the catalytic activities of the dimeric complex, [Ti(Oi-Pr)2(N-alkoxy-β- ketoiminate)]2 and Ti(Oi-Pr)4 were not sensitive to the added solvent. The dimeric complex showed living character, while other catalysts suffered from chain termination reactions.
Keywords
N-Alkoxy-${\beta}$-ketoiminate; Titanium complexes; TEX>${\varepsilon}$-Caprolactone; Ring-opening polymerization; Transesterification;
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