Mesoionic N‐Heterocyclic Olefins as Initiators for the Lewis Pair Polymerization of Epoxides DOI Creative Commons

Iris Haug,

Justus Reitz,

Célia Ziane

et al.

Macromolecular Rapid Communications, Journal Year: 2024, Volume and Issue: 45(12)

Published: March 18, 2024

Abstract Mesoionic N ‐heterocyclic olefins (mNHOs) have recently emerged as a novel class of highly nucleophilic and super‐basic σ‐donor compounds. Making use these properties in synthetic polymer chemistry, it is shown that combination specific mNHO Mg‐based Lewis acid (magnesium bis(hexamethyldisilazide), Mg(HMDS) 2 ) delivers poly(propylene oxide) quantitative yields from the polymerization corresponding epoxide (0.1 mol% loading). The initiation mechanism involves monomer activation by direct ring‐opening attack mNHO, forming zwitterionic propagating species. Modulation thereby tool to impact efficiency, revealing sterically unencumbered triazole‐derivative particularly useful. joint application mNHOs together with borane‐type acids also outlined, resulting high conversions fast kinetics. Importantly, while molar mass distributions remain relatively broad, indicating faster propagation than initiation, overall masses are significantly lower found case regular NHOs, underlining increased nucleophilicity ensuing improved efficiency mNHOs.

Language: Английский

Organoboron-mediated polymerizations DOI
Yao‐Yao Zhang, Guan‐Wen Yang, Chenjie Lu

et al.

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(7), P. 3384 - 3456

Published: Jan. 1, 2024

The scientific community has witnessed extensive developments and applications of organoboron compounds as synthetic elements metal-free catalysts for the construction small molecules, macromolecules, functional materials over last two decades. This review highlights achievements organoboron-mediated polymerizations in past several decades alongside mechanisms underlying these transformations from standpoint polymerization mode. Emphasis is placed on free radical polymerization, Lewis pair ionic (cationic anionic) polyhomologation. Herein, alkylborane/O

Language: Английский

Citations

30

From epoxides and carbon dioxide to polycarbonates: synthesis, properties and applications DOI
Е. В. Черникова, I. P. Beletskaya

Russian Chemical Reviews, Journal Year: 2024, Volume and Issue: 93(2), P. RCR5112 - RCR5112

Published: Jan. 16, 2024

Carbon dioxide (CO<sub>2</sub>) plays a vital role in organic and polymer chemistry as source of cheap available raw material for the synthesis many valuable products, including materials with specified set properties, solvent chemical reactions. This review is devoted to synthesis, properties applications polycarbonates obtained by copolymerization CO<sub>2</sub> epoxides, hot topic that has aroused great interest among scientific community industry representatives. The existing data on catalytic systems used are analyzed summarized, depolymerization polycarbonates, which key aspect recycling, discussed, information systematized, prospects development this area considered.<br> Bibliography — 438 references.

Language: Английский

Citations

8

Insights into the Distinct Behaviors between Bifunctional and Binary Organoborane Catalysts through Terpolymerization of Epoxide, CO2, and Anhydride DOI
Rui Xie, Yuhui Wang, Shuai Li

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(27)

Published: April 22, 2024

Alkyl borane compounds-mediated polymerizations have expanded to Lewis pair polymerization, free radical ionic ring-opening and polyhomologation. The bifunctional organoborane catalysts that contain the acid ammonium or phosphonium salt in one molecule demonstrated superior catalytic performance for polymerization of epoxides copolymerization CO

Language: Английский

Citations

8

Rational Optimization of Ammonium and Phosphonium Cations of Bifunctional Organoborane Catalysts for Copolymerization of Propylene Oxide with CO2 to Afford Poly(propylene carbonate) DOI
Cheng‐Kai Xu, Chenjie Lu, Shuo Zhao

et al.

Macromolecules, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 20, 2024

Language: Английский

Citations

4

The Role of Ligand Exchange in Salen Cobalt Complexes in the Alternating Copolymerization of Propylene Oxide and Carbon Dioxide DOI Open Access
Sergey A. Rzhevskiy, Olga V. Shurupova, Andrey F. Asachenko

et al.

International Journal of Molecular Sciences, Journal Year: 2024, Volume and Issue: 25(20), P. 10946 - 10946

Published: Oct. 11, 2024

A comparative study of the copolymerization racemic propylene oxide (PO) with CO2 catalyzed by (salcy)CoX (salcy = N,N′-bis(3,5-di-tert-butylsalicylidene)-1,2-diaminocyclohexane; X perfluorobenzoate (OBzF5) or 2,4-dinitrophenoxy (DNP)) in presence a [PPN]Cl ([PPN] bis(triphenylphosphine)iminium) cocatalyst is performed bulk at 21 °C and 2.5 MPa pressure CO2. The increase nucleophilicity an attacking anion results rate. Racemic provides high selectivity copolymerization, which can be higher than 99%, living polymerization mechanism. Poly(propylene carbonate) (PPC) bimodal molecular weight distribution (MWD) formed throughout copolymerization. Both modes are characterized low dispersity, while their contribution to MWD depends on nature anion. (salcy)CoDNP/[PPN]DNP system found preferable for production PPC yield selectivity.

Language: Английский

Citations

4

Harnessing Borane-Potassium Cooperativity for Sulfurated Ring-Opening Copolymerisation DOI Creative Commons

R. M. Bhargav,

Kailey Sun Marcus,

Rosa M. Gomila

et al.

Green Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Catalysts combining commercial borane Lewis acids and potassium acetate complexes achieve the selective ring-opening copolymerization (ROCOP) of oxetanes with diverse sulfur-containing monomers.

Language: Английский

Citations

0

Ring‐Opening Polymerization of Epoxides Through Organocatalysis DOI Open Access
Lijun Liu, Yuxuan Zhou, Xingyu Tang

et al.

Published: March 7, 2025

Language: Английский

Citations

0

Organocatalyzed Copolymerization of CO 2 with Epoxide Toward Polycarbonate Synthesis DOI Open Access
Xiaoshuang Feng, Yves Gnanou

Published: March 7, 2025

Language: Английский

Citations

0

Organocatalyzed Ring‐Opening Copolymerization of Cyclic Anhydride and Cyclic Ether (Acetal) DOI Open Access
Xun Zhang, Chengjian Zhang, Xinghong Zhang

et al.

Published: March 7, 2025

Language: Английский

Citations

0

One-Step Hybrid Block Copolymerization by Organocatalysis DOI
Heng Li,

Weihong Zeng,

Zhizhuang Li

et al.

Progress in Polymer Science, Journal Year: 2025, Volume and Issue: unknown, P. 101955 - 101955

Published: March 1, 2025

Language: Английский

Citations

0