From epoxides and carbon dioxide to polycarbonates: synthesis, properties and applications

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

Published: Jan. 16, 2024

Carbon dioxide (CO₂) 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 CO₂ 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

---

Random Terpolymer of Carbon Dioxide, Butadiene and Epoxides: Synthesis, Functionalization and Degradability

Chinese Journal of Chemistry, Journal Year: 2024, Volume and Issue: 42(14), P. 1630 - 1636

Published: March 15, 2024

Comprehensive Summary The utilization of carbon dioxide (CO 2 ) as a C1 feedstock is consistently attractive, especially in the preparation sustainable polymeric materials. In this contribution, terpolymer CO , 1,3‐butadiene (BD) and epoxide synthesized by scandium triflate catalyzed cationic ring‐opening copolymerization α ‐ethylidene‐ δ ‐vinyl‐ ‐valerolactone (EVL), an intermediate derived from BD, with epoxides. obtained content 22 mol% has number‐average molecular weight ( M n up to 7.8 kg/mol dispersity Đ 2.4. reactivity ratios EVL cyclohexene oxide (CHO) are determined 0.01 1.07, respectively, suggesting random characteristic terpolymer. preserved C=C double bonds BD allow for further modification photoinitiated crosslinking. yielded networks fluorescent degradable. This method offers enhanced versatility synthesis additional functionalization ‐based polymers.

Language: Английский

---

Closed‐loop recycling of mixed plastics of polyester and CO2‐based polycarbonate to a single monomer

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(34)

Published: June 4, 2024

Abstract Physical blending is an effective strategy for tailoring polymeric materials to specific application requirements. However, physically blended mixed plastics waste adds additional barriers in mechanical or chemical recycling. This difficulty arises from the intricate requirement meticulous sorting and separation of various polymers inherent incompatibility during To overcome this impediment, work furthers emerging single‐monomer – multiple‐materials approach through design a bifunctional monomer that can not only orthogonally polymerize into two different types specifically lactone‐based polyester CO 2 ‐based polycarbonate but resultant their mixture also be depolymerized back single, original when facilitated by catalysis. Specifically, lactone/epoxide hybrid (BiL O ) undergoes ring‐opening polymerization lactone manifold produce polyester, PE(BiL ), applied copolymerization with , via epoxide manifold, yield polycarbonate, PC(BiL ). Remarkably, one‐pot recycling process BiL ‐derived PE/PC blend constituent >99 % selectivity was achieved superbase catalyst at 150 °C, thereby effectively obviating typically required polymers.

Language: Английский

---

CO2 fixation: cycloaddition of CO2 to epoxides by practical metal-free recyclable catalysts

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

Published: Nov. 25, 2024

Recent works on practical and recyclable catalysts for the cycloaddition of CO 2 to epoxides are reviewed with an eye use inexpensive, readily-available, non-toxic materials future emerging designs.

Language: Английский

---

Correlating Metal Redox Potentials to Co(III)K(I) Catalyst Performances in Carbon Dioxide and Propene Oxide Ring Opening Copolymerization

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(37)

Published: July 6, 2023

Abstract Carbon dioxide copolymerization is a front‐runner CO 2 utilization strategy but its viability depends on improving the catalysis. So far, catalyst structure‐performance correlations have not been straightforward, limiting ability to predict how improve both catalytic activity and selectivity. Here, simple measure of ground‐state parameter, metal reduction potential, directly correlates with polymerization It applied compare performances 6 new heterodinuclear Co(III)K(I) catalysts for propene oxide (PO)/CO ring opening (ROCOP) producing poly(propene carbonate) (PPC). The best shows an excellent turnover frequency 389 h −1 high PPC selectivity >99 % (50 °C, 20 bar, 0.025 mol% catalyst). As demonstration utility, neither DFT calculations nor ligand Hammett parameter analyses are viable predictors. proposed that cobalt redox potential informs upon active site electron density more rich centre showing better performances. method may be widely applicable recommended guide future discovery other (co)polymerizations carbon utilizations.

Language: Английский

---

Development and lifecycle assessment of various low- and high-density polyethylene production processes based on CO2 capture and utilization

Journal of Cleaner Production, Journal Year: 2023, Volume and Issue: 414, P. 137624 - 137624

Published: June 3, 2023

Language: Английский

---

Evaluating Heterodinuclear Mg(II)M(II) (M = Mn, Fe, Ni, Cu, and Zn) Catalysts for the Chemical Recycling of Poly(cyclohexene carbonate)

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(24), P. 15770 - 15778

Published: Nov. 23, 2023

Polymer chemical recycling to monomers (CRM) is important help achieve a circular plastic economy, but the "rules" governing catalyst design for such processes remain unclear. Here, carbon dioxide-derived polycarbonates undergo CRM produce epoxides and dioxide. A series of dinuclear catalysts, Mg(II)M(II) where M(II) = Mg, Mn, Fe, Co, Ni, Cu, Zn, are compared poly(cyclohexene carbonate) depolymerizations. The conducted in solid state, at 140 °C monitored using thermal gravimetric analyses, or performed larger-scale laboratory glassware. most active catalysts are, order decreasing rate, Mg(II)Co(II), Mg(II)Ni(II), Mg(II)Zn(II), with highest activity reaching 8100 h–1 >99% selectivity cyclohexene oxide. Both values yet reported this field, operate low loadings moderate temperatures (from 1:300 1:5000, °C). For best heterodinuclear depolymerization kinetics activation barriers determined. rates both reverse forward CHO/CO2 polymerization catalysis show broadly similar trends, feature different intermediates; depends upon metal–carbonate intermediate, while metal-alkoxide intermediate. These attractive plastics should be prioritized other oxygenated polymers copolymers, including polyesters polyethers. This work provides insights into factors controlling steers future toward exploitation lightweight abundant s-block metals, as Mg(II).

Language: Английский

---

Closing plastic loop with CCUS: Life cycle assessment of a novel strategy for plastic sustainable transition and negative emissions

Resources Conservation and Recycling, Journal Year: 2024, Volume and Issue: 208, P. 107738 - 107738

Published: May 31, 2024

Language: Английский

---

Dual Kinetic Control of Polycarbonate Sequences via Breaking Catalysis Symmetry Using Dual Biomimetic Organoboron Catalysts

Macromolecules, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 17, 2025

Biomimetic catalysis is extensively used in chemical synthesis targeting to achieve satisfactory reactivities. However, artificial catalysts possessing outstanding sequence controllability over macromolecular structures that could be precisely achieved nature remain scarce, especially the preparation of complex macromolecules featuring kinetically trapped structures. Herein, we report a dual biomimetic catalyst design for precise regulation controlled CO2/epoxide copolymerization. The as-synthesized dissymmetric organoboron possess microenvironments, which differentiate transfer rates polymer alkoxy anions between two boron centers, thus enabling regulation. Consequently, high −ABB–/–AB– ratio 92% was achieved, up 3.3 times analogous symmetric (Nat. Synth. 2022, 1, 892–901). Detailed mechanistic studies reveal kinetic modulations are responsible This tactic should inspire effective designs transformations.

Language: Английский

---

Zinc-Catalyzed Carbon Dioxide Based Biodegradable Polycarbonate Synthesis

Synthesis, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 12, 2025

Abstract Carbon dioxide based degradable polycarbonate can be obtained through the copolymerization reaction of carbon with epoxide in presence a catalyst. This polymer has attracted much attention recent years owing to its environmentally friendly and sustainable characteristics, excellent material properties. Due unique properties, CO2-based wide range applications many fields such as electronic electrical parts, automotive medical devices, aerospace equipment, power radiation protection products. Therefore, numerous catalytic systems have been explored for CO2/epoxide process, which zinc catalyst longest history greatest variety. In this short review, significant advances catalysts transformation CO2 are demonstrated, covering both heterogeneous homogeneous catalysts. Moreover, benefits drawbacks system described, outlook large-scale industrial applicati ons future is also represented. 1 Introduction 2 Heterogeneous Zinc Catalysts 3 Homogeneous 4 Overview 5 Conclusion

Language: Английский

---