Alkyl Borane-Mediated Metal-Free Ring-Opening (Co)Polymerizations of Oxygenated Monomers

Carbon dioxide (CO2) is considered a renewable one-carbon building block for chemical synthesis owing to its abundance, low toxicity, nonflammability, and availability. The incorporation of CO2 into the polymer backbone affords various ester- or carbonyl-containing moieties, which create desired material properties and impart unique degradability after use under microbial conditions. In this Perspective, we focus on critical advances in CO2-derived polymers and highlight catalytic strategies, novel conceptual routes, and potential application fields. The outlook and perspective are provided to describe the future challenges and new strategies for establishing CO2-based polymers with desired performances and economic competitiveness comparable to that of petroleum-based materials. 

Current Challenges and Perspectives in CO2-Based Polymers

Tertiary and Quaternary Phosphonium Borane Bifunctional Catalysts for CO2/Epoxide Copolymerization: A Mechanistic Investigation Using In Situ Raman Spectroscopy

Borane Catalysis for Epoxide (Co)Polymerization

The design of reactive species that can either serve to initiate the ring-opening polymerization of epoxides for the synthesis of high molar mass polyethers or be alternatively used to catalyze the synthesis of polyether telechelics in the presence of chain transfer agents has long been an elusive goal. Here, we report the synthesis of a series of bifunctional borinane-based catalysts that enable the living ring-opening polymerization of epoxides with an unprecedented activity (TOF ≥ 1.8 × 105 h–1) and a molar mass up to 106 g/mol under mild conditions. When used along with chain transfer agents to generate low Mn telechelics, the same borinane-based catalysts exhibit high productivity even for loading amounts as low as 50 ppb for ethylene oxide polymerization. These newly designed catalysts also afford the polymerization of oxetane with record TOF values and molar masses. 

/pdf/borinane-boosted-bifunctional-organocatalysts-for-ultrafast-fth2gxor.pdf

Borinane Boosted Bifunctional Organocatalysts for Ultrafast Ring-Opening Polymerization of Cyclic Ethers

Ring-opening polymerization (ROP) is a powerful approach to prepare well-defined polymers. Herein, a one-component Lewis pair strategy was adopted, and two delicate Lewis pairs 1–2 were rationally designed and conveniently synthesized. Lewis pairs 1–2 featured an electropositive phosphonium cation, two electrophilic boron centers involving two 9-borabicyclo[3.3.1]nonane moieties, and a nucleophilic halide (Br– or I–). Lewis pair 1–2-mediated ROP of propylene oxide (PO) exhibited activity (turnover frequency = 3600 h–1) with a living characteristic and low catalyst feeding (0.003 mol %) and afforded an extremely high-molecular-weight α-halide/ω-OH polypropylene oxide (PPO, Mn = 489.5 kg/mol) under mild conditions (−30 to 0 °C). We highlight the success of the one-component Lewis pair strategy to achieve living PO polymerization and extremely high-molecular-weight PPO attributing to two important factors: better control (less transfer reaction) and rapid polymerization kinetics, which takes full advantage of the unique structures and the synergistic effect of 1–2. A preliminary investigation demonstrated that water can be added to the polymerization setup and served as a chain transfer reagent, leading to a controlled polymerization and producing α-hydroxy/ω-OH PPO. The present study provides an insightful mechanistic understanding of the designed one-component Lewis pair systems in epoxide homopolymerization based on spectroscopic data analysis and density functional theory calculations. 

Exploration of the Synergistic Effect in a One-Component Lewis Pair System: Serving as a Dual Initiator and Catalyst in the Ring-Opening Polymerization of Epoxides

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Exploration of the Synergistic Effect in a One-Component Lewis Pair System: Serving as a Dual Initiator and Catalyst in the Ring-Opening Polymerization of Epoxides