High Molar Mass Poly(1,4-butadiene)-graft-poly(ε-caprolactone) Copolymers by ROMP: Synthesis via the Grafting-From Route and Self-Assembling Properties

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• 作者：Flavien Leroux ; Véronique Montembault ; Sandie Piogé ; Sagrario Pascual ; Guillaume Brotons ; Laurent Fontaine
• 刊名：Macromolecules
• 出版年：2016
• 出版时间：July 12, 2016
• 年：2016
• 卷：49
• 期：13
• 页码：4739-4745
• 全文大小：412K
• 年卷期：0
• ISSN：1520-5835

文摘

Well-defined high molar mass poly(1,4-butadiene)-g-poly(ε-caprolactone) (PBu-g-PCL) graft copolymers were prepared through the grafting-from route by the combination of ring-opening metathesis polymerization (ROMP) and organocatalyzed ring-opening polymerization (ROP). The synthesis route relies on the ROMP of cis-4-benzyloxymethyl-3-hydroxymethylcyclobutene initiated by ruthenium-based Grubbs’ catalysts followed by organocatalyzed ROP of ε-caprolactone initiated by the hydroxyl side groups of the backbone using 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) as the catalyst. The reported strategy provides PBu-g-PCL having a strictly poly(1,4-butadiene) backbone with the highest molar mass reported up to now (M_n > 10⁶ g mol^–1). Self-assembling properties of the resulting PBu-g-PCL graft copolymer were investigated using small-angle X-ray scattering (SAXS) in toluene solution and in the solid state.