Under mild conditions, PPO-PEO-PPO ("reverse Pluronics") and PBO-PEO-PBO copolyether were generated by way of N-heterocyclic olefin-based organocatalysis. Reverse Pluronics with molar masses > 20 000 g mol could be synthesized with excellent control (Đ ≤ 1.03) and were converted into (ordered) mesoporous carbons via organic self-assembly to showcase the need for tailor-made copolymer as structure-directing agent.

Using catalyst pairs consisting of N-heteorcyclic olefins (NHOs) and metal-based Lewis acids for the polymerization of lactide, it is possible to precisely control the resulting polymerization mechanism, and NHO placement,...

Herein, N-heterocyclic olefins (NHOs) are utilized as catalysts for the ring-opening polymerization (ROP) of functional aliphatic carbonates. This emerging class of catalysts provides high reactivity and rapid conversion. Aiming for the polymerization of monomers with high side chain functionality, six-membered carbonates derived from 2,2-bis­(hydroxymethyl)­propionic acid (bis-MPA) served as model compounds. Tuning the reactivity of NHO from predominant side chain transesterification at room temperature toward ring-opening at lowered temperatures (−40 °C) enables controlled ROP. These refined conditions give narrowly distributed polymers of the hydrophobic carbonate 5-methyl-5-benzyloxycarbonyl-1,3-dioxan-2-one (MTC-OBn) (Đ < 1.30) at (pseudo)­first-order kinetic polymerization progression. End group definition of these polymers demonstrated by mass spectrometry underlines the absence of side reactions. For the active ester monomer 5-methyl-5-pentafluorophenyloxycarbonyl-1,3-dioxane-2-one (MTC-PFP) with elevated side chain reactivity, a cocatalysis system consisting of NHO and the Lewis acid magnesium iodide is required to retune the reactivity from side chains toward controlled ROP. Excellent definition of the products (Đ < 1.30) and mass spectrometry data demonstrate the feasibility of this cocatalyst approach, since MTC-PFP has thus far only been polymerized successfully using acidic catalysts with moderate control. The broad feasibility of our findings was further demonstrated by the synthesis of block copolymers for bioapplications and their successful nanoparticular assembly. High tolerability of NHO in vitro with concentrations ranging up to 400 μM (equivalent to 0.056 mg/mL) further emphasize the suitability as a catalyst for the synthesis of bioapplicable materials. The polycarbonate block copolymer mPEG44-b-poly­(MTC-OBn) enables physical entrapment of hydrophobic dyes in sub-20 nm micelles, whereas the active ester block copolymer mPEG44-b-poly­(MTC-PFP) is postfunctionalizable by covalent dye attachment. Both block copolymers thereby serve as platforms for physical or covalent modification of nanocarriers for drug delivery.

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