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A novel functional polycarbonate (PAGC), characterized by the presence of double bonds within its side chain, was successfully synthesized through a ternary copolymerization of propylene oxide (PO), allyl glycidyl ether (AGE), and carbon dioxide (CO2). Polyhedral oligomeric silsesquioxanes octamercaptopropyl (POSS-SH) was employed as a crosslinking agent, contributing to the formation of organic–inorganic hybrid materials. This incorporation was facilitated through thiol-ene click reactions, enabling effective interactions between the POSS molecules and the double bonds in the side chains of the polycarbonate. Scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS) confirmed a homogeneous distribution of silicon (Si) and sulfur (S) in the polycarbonate matrix. The thiol-ene click reaction between POSS-SH and the polycarbonate led to a micro-crosslinked structure. This enhancement significantly increased the tensile strength of the polycarbonate to 42 MPa, a notable improvement over traditional poly (propylene carbonate) (PPC). Moreover, the cross-linked structure exhibited enhanced solvent resistance, expanding the potential applications of these polycarbonates in various plastic materials. [ABSTRACT FROM AUTHOR]

Construction of CO2‐based amphiphilic block copolymers (ABCs) is an efficient method for providing CO2‐based polycarbonates with self‐assembly properties in aqueous media. It is challenging to construct CO2‐based ABCs by one‐step strategies from mixed monomers because hydrophilic blocks, usually composed of polar monomers, have negative effects on the synthesis of polycarbonates. In this work, we report a one‐step method to construct CO2‐based ABCs obtained by simultaneous ring‐opening copolymerization (ROCOP) of CO2/epoxides and reversible addition‐fragmentation chain transfer (RAFT) polymerization of N‐isopropyl acrylamide (NIPAM). A trithiocarbonate/carboxy compound was used as the bifunctional chain transfer agent, and an aluminum porphyrin complex was used as the catalyst for ROCOP, which proved to be efficient in CO2 copolymerization even in the presence of NIPAM with strong polarity. This strategy allows flexible control over the molecular weight (5–16 kg/mol) and the hydrophilic‐hydrophobic balance (HLB 9–18) of the ABCs, and ensures narrow polydispersity Đ (1.1–1.3) of the polymers. The ABCs can further self‐assemble into micelles in water with controllable diameters and reversible phase transformation behavior with temperature changes from 25 to 40 °C. This simple route to CO2‐based ABCs with multiple functions has large potential in biomedical applications. [ABSTRACT FROM AUTHOR]

The copolymerization of carbon dioxide (CO2) with epoxides demonstrates promise as a new synthetic method for low-carbon polymer materials, such as aliphatic polycarbonate materials. In this study, a binary Schiff base cobalt system was successfully used to catalyze the copolymerization of 1,2-butylene oxide (BO) and CO2 and its terpolymerization with other epoxides such as propylene oxide (PO) and cyclohexene oxide (CHO). 1H nuclear magnetic resonance (1H NMR), diffusion-ordered spectroscopy (DOSY), gel permeation chromatography (GPC), and differential scanning calorimetry (DSC) confirmed the successful synthesis of the alternating terpolymer. In addition, the effects of the polymerization reaction conditions and copolymerization monomer composition on the polymer structure and properties were examined systematically. By regulating the epoxide feed ratio, polycarbonates with an adjustable glass transition temperature (Tg) (11.2–67.8 °C) and hydrophilicity (water contact angle: 85.2–95.2°) were prepared. Thus, this ternary polymerization method provides an effective method of modulating the surface hydrophobicity of CO2-based polymers and their biodegradation properties. [ABSTRACT FROM AUTHOR]

The incorporation of diverse macromolecular blocks into CO 2 -based polycarbonates offers a promising approach for tailoring the properties of polycarbonates for special needs. In this work, we report for the first time the synthesis and characterization of an ABA triblock copolymer polycarbonate- b -polyalkenamer- b -polycarbonate in combination of ROCOP and ROMP via a one-pot route from CO 2 , epoxides and cycloalkenes. Cis -2-butene-1,4-diol as the bifunctional chain transfer agent was used as a "bridge" for the combination of different blocks as well as an effective regulator for the molecular weight of the polymers. In the one-pot reaction, the conversion of cycloalkenes reached 99.9% within 0.5 h, while the conversion of CHO was initially marginal at 0.5% but gradually increased to 99.7% after 24 h. The significant discrepancy in reaction rates between the two processes enables efficient synergistic reactions within the one-pot system. Specifically, hydroxyl-telechelic polyalkenamer is initially formed via ROMP and subsequently acts as an active species for ROCOP when coordinated with the porphyrin Al catalyst. This one-pot strategy provides a unique and simple method for controllably constructing functional polycarbonates with single-modal molecular weight distributions. By integrating the advantages of polyalkenamers and polycarbonates, this approach proves to be a viable solution for addressing the unsatisfactory thermal properties of aliphatic polycarbonates. [Display omitted] • CO 2 -based functional polycarbonate prepared via one pot reaction in combination of ROCOP and ROMP. • Bifunctional chain transfer agent as a bridge for polycarbonate and polyalkenamer to achieve block copolymer. • ABA block structure confirmed by 1H NMR, DOSY and MALDI-TOF analysis. [ABSTRACT FROM AUTHOR]

CO 2 -based polycarbonates are among the most promising eco-friendly polymers with excellent biodegradability and biocompatibility. However, the poor performance of conventional CO 2 -based polycarbonates such as poly(propylene carbonate) (PPC) and poly(cyclohexene oxide) (PCHC) limits their application. Herein, a series of siloxane functionalized CO 2 -based polycarbonates were obtained via terpolymerization of carbon dioxide (CO 2), propylene oxide (PO), and [2-(3, 4-epoxycyclohexyl)-ethyl] trimethoxysilane (TMSO) using a SalenCoCl/PPNCl catalyst system. A systematic study of these polycarbonate's thermal, mechanical, and surface properties was conducted by tuning the ratio between TMSO and PO. The siloxane units offered polycarbonate with a higher surface energy, resulting in a water contact angle of 110° and a significant improvement in glass transition temperature (T g) and decomposition temperature (T d). Additionally, the micro-crosslinked structure formed by the hydrolysis and condensation of methoxysilane groups provided to the polycarbonate's remarkable mechanical strength, with a high tensile strength of 46 MPa. As a result, a novel CO 2 -based polycarbonate derived from cost-efficient silane coupling agents and CO 2 has shown promising results as an alternative to rigid plastics used in industry. [Display omitted] • Siloxane functionalized polycarbonates were prepared from carbon dioxide and epoxides. • Micro-crosslinked structure of polycarbonate endows its excellent mechanical properties. • Methoxysilane groups increase surface energy and permit post-modification. [ABSTRACT FROM AUTHOR]