New Perspectives in Living/Controlled Anionic Polymerization

Deffieux, Alain; Carlotti, Stéphane; Desbois, Philippe

doi:10.1002/masy.200551104

Cited by 3 publications

(1 citation statement)

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“…The first initiating systems of this type were based on alkali metal alkoxides with trialkyl-aluminum species, resulting in an enhanced polymerization rate and little occurrence of transfer reactions compared to conventional AROP . Improved initiator systems are based on organic salts, containing noncoordinating cations such as tetraalkyl ammonium halides or phosphonium salts combined with triisobutylaluminum as a catalyst, which fully suppress transfer reactions. ,− However, besides the desired initiation via the respective halide anion, concurrent ring opening via hydride or iso -butyl groups is reported, which may lower molecular weights and lead to a fraction of ill-defined chain ends (Scheme e ). , …”

Section: Polymerization Of Alkylene Oxides: Methodsmentioning

confidence: 99%

Polymerization of Ethylene Oxide, Propylene Oxide, and Other Alkylene Oxides: Synthesis, Novel Polymer Architectures, and Bioconjugation

et al. 2015

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The review summarizes current trends and developments in the polymerization of alkylene oxides in the last two decades since 1995, with a particular focus on the most important epoxide monomers ethylene oxide (EO), propylene oxide (PO), and butylene oxide (BO). Classical synthetic pathways, i.e., anionic polymerization, coordination polymerization, and cationic polymerization of epoxides (oxiranes), are briefly reviewed. The main focus of the review lies on more recent and in some cases metal-free methods for epoxide polymerization, i.e., the activated monomer strategy, the use of organocatalysts, such as N-heterocyclic carbenes (NHCs) and N-heterocyclic olefins (NHOs) as well as phosphazene bases. In addition, the commercially relevant double-metal cyanide (DMC) catalyst systems are discussed. Besides the synthetic progress, new types of multifunctional linear PEG (mf-PEG) and PPO structures accessible by copolymerization of EO or PO with functional epoxide comonomers are presented as well as complex branched, hyperbranched, and dendrimer like polyethers. Amphiphilic block copolymers based on PEO and PPO (Poloxamers and Pluronics) and advances in the area of PEGylation as the most important bioconjugation strategy are also summarized. With the ever growing toolbox for epoxide polymerization, a "polyether universe" may be envisaged that in its structural diversity parallels the immense variety of structural options available for polymers based on vinyl monomers with a purely carbon-based backbone.

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Section: Polymerization Of Alkylene Oxides: Methodsmentioning

confidence: 99%

Polymerization of Ethylene Oxide, Propylene Oxide, and Other Alkylene Oxides: Synthesis, Novel Polymer Architectures, and Bioconjugation

et al. 2015

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Ethylene Oxide Polymers: Synthesis, Modification, Topology, and Applications

Shen

Wang

2018

Encyclopedia of Polymer Science and Technology

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This article reviews the synthesis, modification, topology, and applications of ethylene oxide polymers (PEGs). The synthetic strategies presented involve the anionic ring‐opening polymerization, cationic ring‐opening polymerization, coordination polymerization, aluminum‐activated polymerization, and metal‐free polymerization. The modification concerns the m PEG derivatives, telechelic and heterotelechelic PEG. PEGs topologies discussed are focused on the block, star‐shaped, hyperbranched, and dendrimer‐like polymers. Based on the well‐defined modification and topology construction of PEGs, their applications in bioconjugation (or PEGylation) and pharmaceutical field, as well as in solid electrolyte, separation science, and support resins are presented. The article aims to help the readers to comprehensively understand the recent progress on PEGs and motivate further interest on these “evergreen” polymers.

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Controlled Oxyanionic Polymerization of Propylene Oxide: Unlocking the Molecular‐Weight Limitation by a Soft Nucleophilic Catalysis

Fornaciari

Pasini

Coulembier

2022

Macromol. Rapid Commun.

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The oxyanionic ring-opening polymerization of propylene oxide (PO) from an exogenous alcohol activated with benign (complexed) metal-alkali carboxylates is described. The equimolar mixture of potassium acetate (KOAc) and 18-crown-6 ether (18C6) is demonstrated to be the complex of choice for preparing poly(propylene oxide) (PPO) in a controlled manner. In the presence of 18C6/KOAc, hydrogen-bonded alcohols act as soft nucleophiles promoting the PO S N 2 process at room temperature and in solvent-free conditions while drastically limiting the occurrence of parasitic hydrogen abstraction generally observed during the anionic ROP of PO. The resulting PPO displays predictable and unprecedented molar masses (up to 20 kg mol −1 ) with low dispersities (Ð M < 1.1), rendering the 18C6/KOAc complex the most performing activator for the oxyanionic polymerization of PO reported to date. Preliminary studies on the preparation of block and statistical copolyethers are also reported.

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New Perspectives in Living/Controlled Anionic Polymerization

Cited by 3 publications

References 10 publications

Polymerization of Ethylene Oxide, Propylene Oxide, and Other Alkylene Oxides: Synthesis, Novel Polymer Architectures, and Bioconjugation

Polymerization of Ethylene Oxide, Propylene Oxide, and Other Alkylene Oxides: Synthesis, Novel Polymer Architectures, and Bioconjugation

Ethylene Oxide Polymers: Synthesis, Modification, Topology, and Applications

Controlled Oxyanionic Polymerization of Propylene Oxide: Unlocking the Molecular‐Weight Limitation by a Soft Nucleophilic Catalysis

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