Issue 33, 2022

Controlled, one-pot synthesis of recyclable poly(1,3-diene)-polyester block copolymers, catalyzed by yttrium β-diketiminate complexes

Abstract

The one-pot synthesis of well-defined block copolymers of olefins/1,3-dienes and polar monomers, such as cyclic esters and acrylates has long been the focus of intense research. Cationic alkyl rare earth metal catalysts, activated by organoborates, have shown to be promising for the polymerization of isoprene or styrene and ε-caprolactone. In this study, we synthesize a series of yttrium bis(alkyl) complexes supported by simple β-diketiminate ancillary ligands. Subtle changes have been made to the β-diketiminate ligand framework to elucidate the effect of ligand structure on the rate and selectivity of olefin/1,3-diene and cyclic ester polymerization, with small ligand changes having a large impact on the resulting polymerizations. Generation of the active cationic species was easily streamlined by identification of appropriate catalyst : organoborate ratios, allowing for high catalyst efficiencies. Notably, we demonstrate the first cationic rare earth metal alkyl-initiated polymerization of δ-valerolactone and ε-decalactone as well as introduced five new block copolymer morphologies. In addition, selective degradation of the ester block in poly(isoprene-b-caprolactone) enabled recovery of the polyisoprene block with identical spectroscopic and thermal properties. Significantly, recopolymerization of the recovered poly(1,3-diene) with fresh ε-caprolactone reproduced the desired diblocks with nearly identical thermal and physical properties to those of virgin copolymer, illustrating a plausible recycling scheme for these materials.

Graphical abstract: Controlled, one-pot synthesis of recyclable poly(1,3-diene)-polyester block copolymers, catalyzed by yttrium β-diketiminate complexes

Supplementary files

Article information

Article type
Edge Article
Submitted
21 Apr 2022
Accepted
21 Jul 2022
First published
08 Aug 2022
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2022,13, 9515-9524

Controlled, one-pot synthesis of recyclable poly(1,3-diene)-polyester block copolymers, catalyzed by yttrium β-diketiminate complexes

S. C. Kosloski-Oh, Y. Manjarrez, T. J. Boghossian and M. E. Fieser, Chem. Sci., 2022, 13, 9515 DOI: 10.1039/D2SC02265F

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