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

Terpolymerization of Oxetane, CO2, and Isothiocyanates with Bifunctional Catalysts: Synthesis and Degradability of Poly(thioimidocarbonate-trimethylene carbonate)s DOI

Io Yamamoto,

Satoshi Muranaka,

Kunihiro Hirose

et al.

ACS Applied Polymer Materials, Journal Year: 2025, Volume and Issue: unknown

Published: April 15, 2025

Language: Английский

Citations

0
N-Triflylation Enables δ-Valerolactam-Epoxide Alternating Copolymerization DOI

Tao Lai,

Shuanjin Wang, Junpeng Zhao

et al.

ACS Macro Letters, Journal Year: 2025, Volume and Issue: unknown, P. 597 - 602

Published: April 27, 2025

δ-Valerolactam (VL), a six-membered cyclic amide, is easily accessible but hardly polymerizable, unlike other-membered homologues. We have discovered that simple N-triflylation effectively activates VL for undergoing copolymerization with epoxides. The strong electron-withdrawing triflyl group allows mild organobases, in cooperation triethyl borane and an alcohol initiator, to trigger the reaction at room temperature, affording strictly alternating poly(ester-sulfonamide) controlled molar mass low dispersity. method proven applicable variety of epoxides, regardless polarity bulkiness substituents, products exhibit good chemical degradability, thermal/enzymatic stability, wide range glass transition temperatures. study indicates N-sulfonylation ring-opening (alternating) together may build up versatile platform support design construction heteroatom-rich polymers using conventionally nonpolymerizable compounds.

Language: Английский

Citations

0
Synthesis of CO2-based elastomers with tunable glass transition temperatures via a Zinc−Cobalt (III) double metal cyanide catalyst DOI

Shuo Zeng,

Qinghai Zhou, Xianhong Wang

et al.

Polymer, Journal Year: 2025, Volume and Issue: unknown, P. 128562 - 128562

Published: May 1, 2025

Language: Английский

Citations

0
Commercial organic Lewis-pair catalysts for efficient ring-opening polymerization of 1,2-butylene oxide DOI
Xianqiang Zeng,

Chen Liu,

Xue Wang

et al.

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

Published: Jan. 1, 2025

The metal-free Lewis pair catalytic system (Et 3 B and TBPBr) enables to deliver high molecular weight PBO with a narrow polydispersity index allows precise synthesis of low polyols using diols as initiators.

Language: Английский

Citations

0
Creating Remarkably Moisture‐ and Air‐Stable Macromolecular Lewis Acid by Integrating Borane within the Polymer Chain: A Highly Active Catalyst for Homo(co)polymerization of Epoxides DOI

Yanru Gu,

Xinhui Kou, Xiaowu Wang

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(7)

Published: Dec. 29, 2023

Abstract Borane‐based Lewis acids (LA) play an indispensable role in the pair (LP) mediated polymerization. However, most borane‐based LPs are moisture‐ and air‐sensitive. Therefore, development of moisture air‐stable LP is highly desirable. To achieve this goal, concept “aggregation induced enlargement effects” by chemically linking multiple borane within a nanoscopic confinement was conceived to create macromolecular LA. Accordingly, extremely air stable borane, namely, PVP‐1B featuring poly(4‐vinylphenol) backbone, constructed. The concentration active site greatly higher than average due local confinement. enhanced activity observed. Moreover, LA aggregation effects allow its tolerance large amount chain transfer agent. Consequently, showed remarkable efficiency for propylene oxide (PO) polymerization at 25 °C (TOF=27900 h −1 ). Furthermore, it enables generation well‐defined telechelic poly (CHO‐ alt ‐CO 2 ) diol (0.6–15.3 kg/mol) with narrow Đ s via copolymerizing cyclohexene CO 80 °C. This work indicates unifying polymer level shows superior catalytic performance constructing binary, bi(multi)functional systems molecular level. paves new way make functional polyethers.

Language: Английский

Citations

7
Chemoselectivity Streamlines the Approach to Linear and Y-Shaped Thiol-Polyethers Starting from Thiocarboxylic Acids DOI
Lijun Liu, Junpeng Zhao, Guangzhao Zhang

et al.

ACS Macro Letters, Journal Year: 2023, Volume and Issue: 12(9), P. 1185 - 1192

Published: Aug. 8, 2023

Thiol-functionalized polyethers, especially poly(ethylene oxide) (PEO), have extensive applications in biomedicine and materials sciences. Herein, we report a simple one-pot synthesis of α-thiol-ω-hydroxyl polyethers through ring-opening polymerization (ROP) epoxides using thiocarboxylic acid initiators followed by situ aminolysis. The efficient chemoselective metal-free Lewis pair catalyst avoids transthioesterification thus achieving well-controlled molar mass, low dispersity, high end-group fidelity. Kinetic calculation results demonstrated fast-initiation mode the ROP for strong nucleophilicity thiocarboxylate anion its weak interaction with acid. method is expanded α-thiol-ω-dihydroxyl (Y-shaped) PEO virtue stability thioester during ROP. thiol functionality linear/Y-shaped further corroborated intensified gold surface resultant protein resistance behavior.

Language: Английский

Citations

6
A new radical initiation for the ring-opening polymerization of tetrahydrofuran with a radical substitution mechanism DOI
Cheng Wu, Yixuan Liu, Chunsheng Xiao

et al.

Polymer, Journal Year: 2024, Volume and Issue: 300, P. 126984 - 126984

Published: March 30, 2024

Language: Английский

Citations

2
Exploring borinane-based multi-ammonium salts for epoxide (co)polymerization: insights into the structure–activity relationship DOI Creative Commons
Vamshi K. Chidara, Yves Gnanou, Xiaoshuang Feng

et al.

Polymer Chemistry, Journal Year: 2024, Volume and Issue: 15(24), P. 2492 - 2501

Published: Jan. 1, 2024

Three bifunctional borinane-based multi-ammonium salts (N + /B) B, C and D (B 8 N 3 (C 6 )Br ; B 2 10 4 ) were synthesized, the polymerization activities of these catalysts evaluated using catalyst A, NBr, as reference.

Language: Английский

Citations

2
Simple/commercially‐available Lewis acid in anionic ring‐opening polymerization: powerful compounds with multiple applications in macromolecular engineering DOI Creative Commons
Nicolas Illy,

Hong-Qing Fu,

Emma Mongkhoun

et al.

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

Published: Sept. 25, 2024

Abstract Simple and commercially available Lewis acids (LAs) are commonly used catalysts in anionic ring‐opening polymerization (AROP) reactions. In particular, for the AROP of epoxides, addition a acid allows transition from so‐called end‐chain mechanism to monomer‐activated mechanism. The presence LA simultaneously leads decrease reactivity active centers through formation three‐species ate complex activation monomer by coordination oxygen atom oxirane ring. These two effects result both an increase propagation kinetics transfer reactions, which has enabled synthesis high molecular weight polyethers. However, impact goes far beyond these classic effects. They have indeed new functional monomers as well heterotelechelic macromolecules. Also widely copolymerization reactions (statistical, sequential, alternating) can strongly influence composition sequence units Finally, also significantly architecture obtained This review aims list various contributions macromolecular engineering illustrate them with well‐chosen examples.

Language: Английский

Citations

2
Terpolymerization of Propylene Oxide, CO2, and p-Toluenesulfonyl Isocyanate for the Synthesis of Poly(urethane-carbonate): p-Toluenesulfonyl Isocyanate Acts as a Backbiting Suppressor DOI

Satoshi Muranaka,

Io Yamamoto,

Tadashi Ema

et al.

ACS Applied Polymer Materials, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 12, 2024

Terpolymerization of propylene oxide, CO2, and p-toluenesulfonyl isocyanate (TsNCO) was catalyzed by bifunctional AlIII porphyrin catalysts to afford polyurethane-poly(propylene carbonate), PU-PPC, with high CO2 contents up 39 wt %. TsNCO acted as a backbiting suppressor at the initial stage terpolymerization, contributing selective formation PU-PPC. In contrast electrophilicity TsNCO, carbamate anion generated reaction alkoxide intermediate has modest nucleophilicity owing tosyl group, which allows for smooth PU units subsequent elongation PPC on catalyst selectively produce Terpolymers having in 1:1 ratio had glass transition temperature (Tg) 86–104 °C, while those higher Tg values 39–40 °C. Block copolymer PU-b-PPC, synthesized one-pot two-step manner, showed two 45 76 Pure 10% weight loss (Td10) 230 PU-PPC Td10 236–254 They were degradable upon UV light irradiation heat treatment, they resistant acid. The terpolymerization strategy using potentially enables one create CO2-based polymers such plastics elastomers degradability controlled or heat.

Language: Английский

Citations

2