Living ring-opening polymerization of β-butyrolactone initiated by mononuclear zirconium compounds containing sterically hindered<i>N</i>,<i>O</i>-chelate and anionic dimethylamide ligands

Jiang, Jianhui; Choi, Jihyun; Yoon, Sungho

doi:10.1039/d3ra00338h

Cited by 3 publications

(2 citation statements)

References 39 publications

(127 reference statements)

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“…1.03-1.07) was prepared by ROP of β-BL initiated by mononuclear zirconium compounds containing sterically hindered N,O-chelate and anionic dimethylamide ligands. 88 The bifunctional organoboron catalysts were applied for the ROP of β-BL. The end-group analyzes performed by NMR and MALDI-TOF MS, indicates that β-BL ring were opened at the oxygenÀalkyl bond.…”

Section: Homo and Copolymers Of β-Butyrolactonementioning

confidence: 99%

Ring‐opening (co)polymerization strategies of selected oxacyclic monomers to control and provide tailored polymers with desired properties

Trzebicka,

Wałach,

Kurcok

et al. 2024

Polymers for Advanced Techs

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Ring‐opening polymerization (ROP) is a versatile synthetic method used to produce polymers from cyclic monomers, particularly oxacyclic monomers such as lactones and cyclic ethers. Oxacyclic monomers polymerize with anionic or cationic initiators. For selected monomers, such as glycidol, β‐butyrolactone and higher lactones, methods, and mechanisms of polymerization are presented, the understanding of which has allowed control of these processes. The use of appropriate polymerization techniques and methods, as well as conducting the copolymerization, mainly block copolymerization, makes it possible to control the architecture, molar mass, and end groups of the resulting polymers. These parameters determine the properties of macromolecules, such as solubility, ability to aggregate in aqueous solutions, thermoresponsiveness, and degradability. By carefully selecting monomers, catalysts, and polymerization conditions, ROP strategies can be tailored to produce polymers with precise molecular structures and desired properties for a wide range of applications. This review mainly focuses on precisely controlled syntheses that lead to well‐defined macromolecules consisting mostly of polyether and/or polyester chains.

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Section: Homo and Copolymers Of β-Butyrolactonementioning

confidence: 99%

Ring‐opening (co)polymerization strategies of selected oxacyclic monomers to control and provide tailored polymers with desired properties

Trzebicka,

Wałach,

Kurcok

et al. 2024

Polymers for Advanced Techs

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“…[ 30 ] Recently, our group achieved controlled living ROP of β‐lactones using a colorless Zr(IV) complex (Chart 1E), synthesized through a facile procedure, yielding polymers with remarkably narrow polydispersity indexes (PDIs) ranging from 1.03 to 1.07. [ 31 ] A very recent research by Williams et al . presented a new heteroleptic Zr(IV) complex (Chart 1F) demonstrat‐ing proficient ring opening co‐polymerization of epoxide/oxetane, tetrahydrofuran, and anhydride with excellent rates, selectivity, and control.…”

Section: Background and Originality Contentmentioning

confidence: 99%

Chloride‐Bridged Dimeric SalphenZr(IV) Cobaltate Catalyst Unleashes the Potential of Base‐Free Carbonylative Polymerization for Biodegradable PHAs^†

Ganesan,

Yoon

2023

Chin. J. Chem.

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Comprehensive SummaryPoly(3‐hydroxyalkanoates) (PHA) are a promising class of biodegradable polymers, exhibiting properties comparable to traditional petroleum‐based counterparts. Nonetheless, the widespread commercialization of PHAs is hindered by the absence of an efficient and economically viable catalytic system, impeding their competitiveness against non‐biodegradable polymers. In an effort to address this challenge, we present a study on a newly developed chloro‐bridged dimeric salphen zirconium cobaltate complex for the direct synthesis of PHAs via carbonylative polymerization of epoxides. The catalytic system demonstrates favorable activity under mild reaction conditions, enabling complete monomer conversion and an impressive 92% selectivity towards PHA formation. Through meticulous control experiments and mechanistic studies, we have gained crucial insights into the polymerization process. Remarkably, our findings challenge the prevailing notion of sequential ring‐opening polymerization of in‐situ generated β‐lactones as the primary pathway. Instead, we demonstrate that the polymerization predominantly proceeds through direct co‐polymerization of epoxide and carbon monoxide, unveiling a novel and efficient mechanism for PHA synthesis.This article is protected by copyright. All rights reserved.

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Bio-Based and Biodegradable Polymeric Materials for a Circular Economy

Oliver-Cuenca,

Salaris,

Muñoz-Gimena

et al. 2024

Polymers

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Nowadays, plastic contamination worldwide is a concerning reality that can be addressed with appropriate society education as well as looking for innovative polymeric alternatives based on the reuse of waste and recycling with a circular economy point of view, thus taking into consideration that a future world without plastic is quite impossible to conceive. In this regard, in this review, we focus on sustainable polymeric materials, biodegradable and bio-based polymers, additives, and micro/nanoparticles to be used to obtain new environmentally friendly polymeric-based materials. Although biodegradable polymers possess poorer overall properties than traditional ones, they have gained a huge interest in many industrial sectors due to their inherent biodegradability in natural environments. Therefore, several strategies have been proposed to improve their properties and extend their industrial applications. Blending strategies, as well as the development of composites and nanocomposites, have shown promising perspectives for improving their performances, emphasizing biopolymeric blend formulations and bio-based micro and nanoparticles to produce fully sustainable polymeric-based materials. The Review also summarizes recent developments in polymeric blends, composites, and nanocomposite plasticization, with a particular focus on naturally derived plasticizers and their chemical modifications to increase their compatibility with the polymeric matrices. The current state of the art of the most important bio-based and biodegradable polymers is also reviewed, mainly focusing on their synthesis and processing methods scalable to the industrial sector, such as melt and solution blending approaches like melt-extrusion, injection molding, film forming as well as solution electrospinning, among others, without neglecting their degradation processes.

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Living ring-opening polymerization of β-butyrolactone initiated by mononuclear zirconium compounds containing sterically hinderedN,O-chelate and anionic dimethylamide ligands

Abstract: The ring-opening polymerization of β-lactones into polyhydroxyalkanoates (PHA), biodegradable polymers with high molecular weight and narrow polydispersity, is of significant interest.

Cited by 3 publications

References 39 publications

Ring‐opening (co)polymerization strategies of selected oxacyclic monomers to control and provide tailored polymers with desired properties

Ring‐opening (co)polymerization strategies of selected oxacyclic monomers to control and provide tailored polymers with desired properties

Chloride‐Bridged Dimeric SalphenZr(IV) Cobaltate Catalyst Unleashes the Potential of Base‐Free Carbonylative Polymerization for Biodegradable PHAs^†

Bio-Based and Biodegradable Polymeric Materials for a Circular Economy

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Living ring-opening polymerization of β-butyrolactone initiated by mononuclear zirconium compounds containing sterically hinderedN,O-chelate and anionic dimethylamide ligands

Abstract: The ring-opening polymerization of β-lactones into polyhydroxyalkanoates (PHA), biodegradable polymers with high molecular weight and narrow polydispersity, is of significant interest.

Cited by 3 publications

References 39 publications

Ring‐opening (co)polymerization strategies of selected oxacyclic monomers to control and provide tailored polymers with desired properties

Ring‐opening (co)polymerization strategies of selected oxacyclic monomers to control and provide tailored polymers with desired properties

Chloride‐Bridged Dimeric SalphenZr(IV) Cobaltate Catalyst Unleashes the Potential of Base‐Free Carbonylative Polymerization for Biodegradable PHAs†

Bio-Based and Biodegradable Polymeric Materials for a Circular Economy

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Product

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About

Chloride‐Bridged Dimeric SalphenZr(IV) Cobaltate Catalyst Unleashes the Potential of Base‐Free Carbonylative Polymerization for Biodegradable PHAs^†