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Fluoride-promoted carbonylation polymerization: a facile step-growth technique to polycarbonates.

ABSTRACT: Fluoride-Promoted Carbonylation (FPC) polymerization is herein presented as a novel catalytic polymerization methodology that complements ROP and unlocks a greater synthetic window to advanced polycarbonates. The overall two-step strategy is facile, robust and capitalizes on the synthesis and step-growth polymerization of bis-carbonylimidazolide and diol monomers of 1,3- or higher configurations. Cesium fluoride (CsF) is identified as an efficient catalyst and the bis-carbonylimidazolide monomers are synthesized as bench-stable white solids, easily obtained on 50-100 g scales from their parent diols using cheap commercial 1,1'-carbonyldiimidazole (CDI) as activating reagent. The FPC polymerization works well in both solution and bulk, does not require any stoichiometric additives or complex settings and produces only imidazole as a relatively low-toxicity by-product. As a proof-of-concept using only four diol building-blocks, FPC methodology enabled the synthesis of a unique library of polycarbonates covering (i) rigid, flexible and reactive PC backbones, (ii) molecular weights 5-20 kg mol^-1, (iii) dispersities of 1.3-2.9 and (iv) a wide span of glass transition temperatures, from -45 up to 169 °C.

SUBMITTER: Olsson JV

PROVIDER: S-EPMC5603846 | biostudies-literature | 2017 Jul

REPOSITORIES: biostudies-literature

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Fluoride-promoted carbonylation polymerization: a facile step-growth technique to polycarbonates.

Olsson J V JV Hult D D García-Gallego S S Malkoch M M

Chemical science 20170504 7

Fluoride-Promoted Carbonylation (FPC) polymerization is herein presented as a novel catalytic polymerization methodology that complements ROP and unlocks a greater synthetic window to advanced polycarbonates. The overall two-step strategy is facile, robust and capitalizes on the synthesis and step-growth polymerization of bis-carbonylimidazolide and diol monomers of 1,3- or higher configurations. Cesium fluoride (CsF) is identified as an efficient catalyst and the bis-carbonylimidazolide monomer ...[more]

PMID: 28959408

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Project description: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.

Dataset Information

Fluoride-promoted carbonylation polymerization: a facile step-growth technique to polycarbonates.

Publications

Fluoride-promoted carbonylation polymerization: a facile step-growth technique to polycarbonates.

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