Ultra-Productive Upcycling CO₂ into Polycarbonate Polyols via Borinane-Based Bifunctional Organocatalysts

Abstract

We herein report the synthesis of commercially attractive low molar mass polycarbonate polyols obtained through the ring-opening copolymerization of CO 2 and epoxides, using a series of borinane-based bifunctional organocatalysts in the presence of chain transfer agents (CTAs). These catalysts enable CO 2 /epoxide copolymerizations with high linear vs cyclic selectivity and outstanding productivity for both poly(cyclohexane carbonate) polyols (18.2 kg/g catalyst) and poly(ether propylene carbonate) polyols (1.1 kg/g catalyst). These copolymerizations exhibit all features of living processes; the molar mass of the resulting polycarbonates could be precisely controlled by varying the [monomer]/CTA ratio. The high performance of these catalysts implying a low loading shows a great potential for applications in large-scale preparation of CO 2 -based polyols.

Synthesis of degradable polyacetals via an intramolecular phosphonium bisborane Lewis pair catalyzed copolymerization of epoxides with o‐phthaladehyde

“…However, the catalytic efficiency was relatively low and the molecular weight of the reported copolymer needed further improvements. In contrast to binary organoborane based Lewis pair, we and others showed that one‐component organoborane based Lewis pair exhibited enhanced activity in the ROP 35,36,39–43 …”

“…In contrast to binary organoborane based Lewis pair, we and others showed that one-component organoborane based Lewis pair exhibited enhanced activity in the ROP. 35,36,[39][40][41][42][43] To diversify the reaction scope of ROAP and demonstrate the synergistic effects on enhancing the activity of one-component organoborane based Lewis pair, we herein attempted to apply PBB-Br for the copolymerization of PO and OPA to generate degradable PPO with acetal backbone.…”

A Supported Catalyst that Enables the Synthesis of Colorless CO2‐Polyols with Ultra‐Low Molecular Weight

“…In contrast, the heterogeneous double metal cyanide catalyst has the potential in the preparation of colorless CO 2 ‐polyol, whereas the molecular weight is hard to below 1200 g mol −1 [13] . Very recently, Feng and Gnanou reported borinane‐based bifunctional organocatalysts ( p =200), achieving a low molecular weight of 1600 g mol −1 [14] . Collectively, it remains challenging to prepare colorless ULMW CO 2 ‐polyols (<1000 g mol −1 ), which is useful for the synthesis of rigid polyurethane foams (high crosslinking density).…”

“…[13] Very recently, Feng and Gnanou reported borinane-based bifunctional organocatalysts (p = 200), achieving a low molecular weight of 1600 g mol À 1 . [14] Collectively, it remains challenging to prepare colorless ULMW CO 2 -polyols (< 1000 g mol À 1 ), which is useful for the synthesis of rigid polyurethane foams (high crosslinking density).…”

Bio-based polycarbonates: progress and prospects

“…In addition, many reviews have summarized the progress of research on aromatic polycarbonates synthesized from BPA and diphenyl carbonate and aliphatic polycarbonates synthesized from epoxide and CO 2 . [37][38][39][40][41][42][43][44][45] However, there are no reviews that provide a systematic summary of bio-based PCs to our knowledge. So in this review, we give a comprehensive introduction to two representative bio-based PCs, poly(isosorbide carbonate)s and poly(limonene carbonate)s. A brief introduction of the bioderived monomers is presented in the rst section.…”