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, Journal Year: 2024, Volume and Issue: 136(27)

Published: April 22, 2024

Abstract 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 2 than their two‐component analogues, i.e., blend salt. To explore origin differences one‐component catalysts, here we conducted a systematic investigation on performances these two kinds via terpolymerization epoxide, carbon dioxide anhydride. resultant terpolymers produced independently by binary catalyst exhibited distinct microstructures, where series gradient polyester‐polycarbonate with varying polyester content were afforded using catalyst, while tapering diblock obtained system. enhances competitiveness insertion anhydride, which leads premature incorporation into polymer chains ultimately results formation terpolymers. DFT calculations revealed role electrostatic interaction charge distribution caused intramolecular synergistic effect catalyst.

Language: Английский

Current Challenges and Perspectives in CO2-Based Polymers DOI
Ye Liu, Xiao‐Bing Lu

Macromolecules, Journal Year: 2023, Volume and Issue: 56(5), P. 1759 - 1777

Published: Feb. 28, 2023

Carbon dioxide (CO2) is considered a renewable one-carbon building block for chemical synthesis owing to its abundance, low toxicity, nonflammability, and availability. The incorporation of CO2 into the polymer backbone affords various ester- or carbonyl-containing moieties, which create desired material properties impart unique degradability after use under microbial conditions. In this Perspective, we focus on critical advances in CO2-derived polymers highlight catalytic strategies, novel conceptual routes, potential application fields. outlook perspective are provided describe future challenges new strategies establishing CO2-based with performances economic competitiveness comparable that petroleum-based materials.

Language: Английский

Citations

51
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

27
Advances in the Synthesis of Chemically Recyclable Polymers DOI

Xin‐Lei Li,

Kai Ma, Fei Xu

et al.

Chemistry - An Asian Journal, Journal Year: 2023, Volume and Issue: 18(3)

Published: Jan. 9, 2023

Abstract The development of modern society is closely related to polymer materials. However, the accumulation materials and their evolution in environment causes not only serious environmental problems, but also waste resources. Although physical processing can be used reuse polymers, properties resulting polymers are significantly degraded. Chemically recyclable a type that degrades into monomers, an effective solution degradation caused by recycling polymers. ideal chemical i. e., quantitative conversion monomers at low energy consumption repolymerization formed with comparable original, attractive research goal. In recent years, significant progress has been made design enabling regulation “polymerization‐depolymerization” equilibrium closed‐loop under mild conditions. This review will focus on following aspects poly(sulfur) esters, polycarbonates, polyacetals, polyolefins, poly(disulfide) polymer, illustrate challenges this area, provide outlook future directions.

Language: Английский

Citations

33
Key progresses of MOE key laboratory of macromolecular synthesis and functionalization in 2022 DOI

Xumeng Deng,

Kaihao Chen, Kai Pang

et al.

Chinese Chemical Letters, Journal Year: 2023, Volume and Issue: 35(3), P. 108861 - 108861

Published: July 27, 2023

Language: Английский

Citations

25
Quantifying CO2 Insertion Equilibria for Low-Pressure Propene Oxide and Carbon Dioxide Ring Opening Copolymerization Catalysts DOI Creative Commons
Katharina H.S. Eisenhardt,

Francesca Fiorentini,

Wouter Lindeboom

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(15), P. 10451 - 10464

Published: April 8, 2024

While outstanding catalysts are known for the ring-opening copolymerization (ROCOP) of CO2 and propene oxide (PO), few reported at low pressure. Here, a new series Co(III)M(I) heterodinuclear compared. The Co(III)K(I) complex shows best activity (TOF = 1728 h–1) selectivity (>90% polymer, >99% CO2) is highly effective pressures (<10 bar). insertion prerate determining chemical equilibrium step. At pressures, concentration active catalyst depends on pressure; above 12 bar, its saturated, rates independent pressure, allowing constant to be quantified first time (Keq 1.27 M–1). A unified rate law, applicable under all operating conditions, presented. As proof potential, published data leading literature reinterpreted constants estimated, showing that this law applies other systems.

Language: Английский

Citations

13
Evolution of Copolymers of Epoxides and CO2: Catalysts, Monomers, Architectures, and Applications DOI
Guan‐Wen Yang, Rui Xie, Yao‐Yao Zhang

et al.

Chemical Reviews, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 25, 2024

The copolymerization of CO

Language: Английский

Citations

11
Toughening CO2‐Derived Copolymer Elastomers Through Ionomer Networking DOI Creative Commons
Kam C. Poon, Georgina L. Gregory, Gregory S. Sulley

et al.

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(36)

Published: May 18, 2023

Abstract Utilizing carbon dioxide (CO 2 ) to make polycarbonates through the ring‐opening copolymerization (ROCOP) of CO and epoxides valorizes recycles reduces pollution in polymer manufacturing. Recent developments catalysis provide access with well‐defined structures allow for biomass‐derived monomers; however, resulting material properties are underinvestigated. Here, new types ‐derived thermoplastic elastomers (TPEs) described together a generally applicable method augment tensile mechanical strength Young's modulus without requiring re‐design. These TPEs combine high glass transition temperature ( T g amorphous blocks comprising poly(carbonates) (A‐block), low poly( ε ‐decalactone), from castor oil, (B‐block) ABA structures. The poly(carbonate) selectively functionalized metal‐carboxylates where metals Na(I), Mg(II), Ca(II), Zn(II) Al(III). colorless polymers, featuring <1 wt% metal, show tunable thermal ), (elongation at break, elasticity, creep‐resistance) properties. best >50‐fold higher 21‐times greater strength, compromise elastic recovery, compared starting block polymers. They have wide operating temperatures (−20 200 °C), creep‐resistance yet remain recyclable. In future, these materials may substitute high‐volume petrochemical be utilized high‐growth fields like medicine, robotics, electronics.

Language: Английский

Citations

18
Catalysis Conversion of Carbon Dioxide and Epoxides by Tetrahydroxydiboron To Prepare Cyclic Carbonates DOI
Yu‐Hui Luo, Fei Chen, Hao Zhang

et al.

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(22), P. 15717 - 15725

Published: Oct. 27, 2023

A binary catalytic system comprising tetrahydroxydiboron and tetrabutylammonium iodide (TBAI) was used to catalyze the cycloaddition of carbon dioxide (CO2) with epoxides. The catalyst (9 mol %), in combination use TBAI (13.5 %) as a nucleophile, is capable catalyzing CO2 various terminal epoxides under room temperature balloon. In addition, range internal epoxides, including sterically hindered bicyclic vegetable oil-based were suitable for system, affording series cyclic carbonates moderate high yields. tetrahydroxydiboron/TBAI cooperative mechanism elucidated using Fourier transform infrared spectroscopy, nuclear magnetic resonance, electrospray ionization-high-resolution mass spectrometry. Results reveal that exhibits dual effects, activating both epoxides; initially, it underwent insertion form boron–CO2 adduct subsequently activated through interaction B–O bond.

Language: Английский

Citations

18
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

7
A one-pot approach towards polycarbonate-b-polyester block copolymers via chemoselective polymerization catalyzed by a one-component phosphonium borane Lewis pair DOI
Yutao Li, Xinhui Kou, Xiaowu Wang

et al.

Polymer Chemistry, Journal Year: 2024, Volume and Issue: 15(24), P. 2476 - 2481

Published: Jan. 1, 2024

Chemoselective polymerization from a mixture of l -LA, CHO and CO 2 enables the synthesis PLLA, PCHC or PCHC- b -PLLA achieved by PBB-Br. The chemoselectivity depends on nature growing polymer chain end.

Language: Английский

Citations

5