Bio-based Polycarbonates Research Articles

Green and Efficient Synthesis of Biobased Polycarbonates with Tunable Performance via Functionalized Ionic Liquid Catalysts Enhanced by Cation–π Interactions

Green and Efficient Synthesis of Biobased Polycarbonates with Tunable Performance via Functionalized Ionic Liquid Catalysts Enhanced by Cation–π Interactions

Synthesis and Properties of Bio-Based Polycarbonates Containing Silicone Blocks.

This study aims to investigate the effects of different hydroxy-terminated silicones on the properties of polycarbonate-silicone copolymers (ICS-PC) by introducing flexible and hydrophobic silicone into isosorbide-based polycarbonate through melt transesterification- polycondensation method. Through compatibility and transesterification experiments, it is confirmed that the alcohol-hydroxyl polydimethylsiloxane (a-PDMS) has higher reactivity and silicone conversion than the phenol-hydroxyl polydimethylsiloxane (p-PDMS), but the conversion does not exceed 81%. Polyether-modified silicone (PEMS) exhibits better compatibility and higher reactivity, thus resulting in higher conversion that can reach 86%. Effects of the type and content of silicone on the glass transition temperature (Tg), optical transparency, saturated water absorption, and mechanical strength of ICS-PCs were also discussed. It is found that p-PDMS has higher Tg, hydrophobicity, and mechanical strength with similar silicone content, but the total transmittance does not exceed 60%. In contrast, the PEMS system exhibits better optical transparency due to its improved compatibility with the PC matrix, with a total transmittance of up to 73%, Tg exceeding 150 °C while maintaining excellent flexibility and hydrophobicity. These results are helpful to further improve the comprehensive properties of bio-based polycarbonates.

Design and Synthesis of Optical Biobased Polycarbonates with High Refractive Index and Low Birefringence

Design and Synthesis of Optical Biobased Polycarbonates with High Refractive Index and Low Birefringence

Ru]-Catalyzed Olefin Metathesis and Ethenolysis for the Synthesis and Recycling of Bio-Based Polycarbonates and Polycyanurates

Eugenol, an abundant, naturally occurring phenolic compound, was converted into a thermoplastic polycarbonate by olefin metathesis followed by interfacial polymerization with triphosghene. This resulted in polymers with Mn ranging from...

Green Synthesis of UV-Reactive Polycarbonates from Levoglucosenone and 5-Hydroxymethyl Furfural.

This study focuses on the synthesis of fully renewable polycarbonates (PCs) starting from cellulose-based platform molecules levoglucosenone (LGO) and 2,5-bis(hydroxymethyl)furan (BHMF). These unique bio-based PCs are obtained through the reaction of a citronellol-containing triol (Triol-citro) derived from LGO, with a dimethyl carbonate derivative of BHMF (BHMF-DC). Solvent-free polymerizations are targeted to minimize waste generation and promote an eco-friendly approach with a favorable environmental factor (E-factor). The choice of metal catalyst during polymerization significantly influences the polymer properties, resulting in high molecular weight (up to 755kDa) when Na2 CO3 is employed as an inexpensive catalyst. Characterization using nuclear magnetic resonance confirms the successful incorporation of the furan ring and the retention of the terminal double bond of the citronellol pendant chain. Furthermore, under UV irradiation, the presence of both citronellol and furanic moieties induces singular structural changes, triggering the formation of three distinct structures within the polymer network, a phenomenon herein occurs for the first time in this type of polymer. These findings pave the way to new functional materials prepared from renewable monomers with tunable properties.

Efficient Synthesis of High-Molecular-Weight Biobased Polycarbonates by Lithium Lactate

Efficient Synthesis of High-Molecular-Weight Biobased Polycarbonates by Lithium Lactate

Biodegradable polycarbonates from lignocellulose based 4-pentenoic acid and carbon dioxide.

The production of biodegradable polycarbonate by copolymerizing CO2 with epoxides has emerged as an effective method to utilize CO2 in response to growing concerns about CO2 emissions and plastic pollution. Previous studies have mainly focused on the preparation of CO2-based polycarbonates from petrochemical-derived propylene oxide (PO) or cyclohexene oxide (CHO). However, to reduce dependence on fossil fuels, the development of 100% bio-based polymers has gained attention in polymer synthesis. Herein, we reported the synthesis of glycidyl 4-pentenoate (GPA) from lignocellulose based 4-pentenoic acid (4-PA), which was further copolymerized with CO2 using a binary catalyst SalenCoCl/PPNCl to produce bio-based polycarbonates with vinyl side chains and molecular weights up to 17.1kg/mol. Introducing a third monomer, PO, allows for the synthesis of the GPA/PO/CO2 terpolymer, and the glass transition temperature (T g) of the terpolymer can be adjusted from 2°C to 19°C by controlling the molar feeding ratio of GPA to PO from 7:3 to 3:7. Additionally, post-modification of the vinyl side chains enables the production of functional polycarbonates, providing a novel approach to the preparation of bio-based materials with diverse side chains and functions.

Bio-based polycarbonates: progress and prospects

The review covers the advancements in bio-based polycarbonates with regards to their raw materials, polymerization techniques, and modification strategies.

Plastics to fertilizer: guiding principles for functionable and fertilizable fully bio-based polycarbonates

Bio-based polycarbonates, copolymers of isosorbide and 1,3:4,6-di-O-benzylidene-d-mannitol, were successfully converted to fertilizerviaammonolysis.

Efficient synthesis of camphor-based polycarbonates: a direct route to recyclable polymers

A commercially available magnesium catalyst is active as a polymerization and depolymerization catalyst, allowing access to bio-based polycarbonates and their recycling by methanolysis.

Choline Chloride/Urea Deep Eutectic Solvents: A Promising Reaction Medium for the Synthesis of Bio-Based Poly(hydroxyurethane)s.

The development of more sustainable and eco-friendly polymers has attracted much attention from researchers over the past decades. Among the different strategies that can be implemented towards this goal, the substitution of the toxic reagents/monomers often used in polyurethane chemistry has stimulated much innovation leading to the development of the hydroxylated version of PURs, namely, the poly(hydroxyurethane)s (PHURs). However, some PHURs remain far from being sustainable as their synthesis may involve monomers and/or solvents displaying poor environmental impacts. Herein, we report on the use of more sustainable conditions to synthesize the biobased polycarbonates involved in the aminolysis reaction. In addition, we demonstrate that the use of renewable deep eutectic solvents (DESs) can act both as excellent solvents and organocatalysts to promote the aminolysis reaction.

Concerning Synthesis of New Biobased Polycarbonates with Curcumin in Replacement of Bisphenol A and Recycled Diphenyl Carbonate as Example of Circular Economy.

Curcumin (CM) is a natural polyphenol well-known for its antioxidant and pharmaceutical properties, that can represent a renewable alternative to bisphenol A (BPA) for the synthesis of bio-based polycarbonates (PC). In the presented strategy, preparation of the CM-based PC was coupled with chemical recycling of the fossil-based BPA polycarbonate (BPA-PC) conducting a two-steps trans-polymerization that replaces BPA monomer with CM or its tetrahydrogenated colorless product (THCM). In the first step of synthetic strategy, depolymerization of commercial BPA-PC was carried out with phenol as nucleophile, according to our previous procedure based on zinc derivatives and ionic liquids as catalysts, thus producing quantitatively diphenyl carbonate (DPC) e BPA. In the second step, DPC underwent a melt transesterification with CM or THCM monomers affording the corresponding bio-based polycarbonates, CM-PC and THCM-PC, respectively. THCM was prepared by reducing natural bis-phenol with cyclohexene as a hydrogen donor and characterized by 1H-NMR and MS techniques. Polymerization reactions were monitored by infrared spectroscopy and average molecular weights and dispersity of the two biobased polymers THCM-PC and CM-PC were determined by means of gel permeation chromatography (GPC). Optical properties of the prepared polymers were also measured.

Alkyl carbonate derivatives of furanics: A family of bio-based stable compounds

Several alkyl carbonate derivatives of 5-hydroxymethylfurfural (HMF) and 2,5-bis(hydroxymethyl)furan (BHMF) have been synthesized for the first time. In most cases high yields were achieved using mild reaction conditions and compounds were recovered as pure with none or minimal purification. The new HMF and BHMF derived products resulted stable over time and they are suitable monomers for new bio-based polycarbonates and polyurethanes.

One-pot synthesis of bio-based polycarbonates from dimethyl carbonate and isosorbide under metal-free condition

A synthetic strategy for bio-based polycarbonate was developed via one-pot polymerization of renewable monomer isosorbide and dimethyl carbonate using eco-friendly organo-catalysts.

Rigid biobased polycarbonates with good processability based on a spirocyclic diol derived from citric acid

A bicylic diketone is derived from citric acid and readily ketalized with trimethylolpropane to produce a spirodiol monomer for rigid, high-molecular weight, melt processable biobased polycarbonates.

Innovative sustainable conversion from CO2 and biodiesel-based crude glycerol waste to bio-based polycarbonates

An innovative and sustainable conversion to produce bio-based polycarbonates from carbon dioxide (CO2) and crude glycerol-fatty acids waste were developed. Crude glycerol, the byproduct of industrial biodiesel process, mainly composed of fatty acids, glycerol, and impurities. Bio-based Epoxide monomers were successfully produced from fatty acids residues waste from crude glycerol refining process with bio-based ephichlorohydrin derived from refined crude glycerol donating epoxy group. Bio-based polycarbonates were successfully synthesized through copolymerizing CO2 and obtained bio-based epoxide monomers, giving carbonate linkages of 98.1%. The effects of impurities from raw crude glycerol on the properties of obtained bio-based polycarbonates were found to be trivial. The bio-based polycarbonates plastic film exhibited good transparency, stable thermal property (thermal decomposition at ˜230 °C), and good mechanical properties (tensile strength of 1.69 MPa, elongation of 59.6%). This developed innovative conversion may provide a new platform to convert CO2 and industrial residues wastes to biodegradable bio-based plastics, affording solutions for environmental challenges.

Ultrasonic and Catalyst-Free Epoxidation of Limonene and Other Terpenes Using Dimethyl Dioxirane in Semibatch Conditions

Limonene dioxide is a key intermediate molecule for the development of biobased polycarbonates or nonisocyanate polyurethanes. In this work the epoxidation of limonene to limonene dioxide using in-situ-generated dimethyl dioxirane as the oxidizing agent under both conventional agitation and ultrasound has been compared. The time required to completely convert limonene to limonene dioxide with 100% yield using ultrasound was only 4.5 min at room temperature. In comparison, when conventional agitation using a magnetic stirrer is used, the required time to reach a 97% yield of limonene dioxide was 1.5 h. The epoxidation of α-pinene has also been studied using both agitation techniques. Epoxidation of α-pinene to α-pinene oxide under ultrasound required only 4 min with an obtained yield of 100%, while in comparison with the conventional method the reaction time was 60 min. As for other terpenes, β-pinene was converted to β-pinene oxide in only 4 min whereas farnesol yielded 100% of the triepoxide in 8 min. Ca...

Bio-derived polymers for coating applications: comparing poly(limonene carbonate) and poly(cyclohexadiene carbonate)

Two fully bio-based polycarbonates, poly(limonene carbonate) and poly(cylcohexadiene carbonate), were post-functionalized via thiol–ene reactions and tested as future coating materials.

Terpolymers Derived from Limonene Oxide and Carbon Dioxide: Access to Cross-Linked Polycarbonates with Improved Thermal Properties

The formation of bio-derived materials is gaining momentum in academic and industrial research as a consequence of depleting petroleum resources, providing mid- and long-term alternative sustainable materials. In this context, we have prepared a series of terpolymers derived from the renewable terpene limonene producing polycarbonates with a controlled and variable ratio of incorporated nonfunctional cyclohexene oxide (CHO) and functional limonene oxide (LO) monomers. As catalyst, a simple binary combination of an Al(III) aminotriphenolate complex and PPNCl (PPN = bis(triphenyl)phosphine–ammonium) has been used to afford the targeted, partially bio-based polycarbonates with typically high carbonate content (>95%), good conversions, and a controllable amount of olefinic groups in the terpolymer backbone. Cross-linked polymers (CLP) have been easily obtained from these terpolymers through thiol–ene click reactions allowing for the preparation of interconnected networks with improved thermal properties with ...

Bio-based polycarbonates derived from the neolignan honokiol

Honokiol, a highly functional phenolic- and alkenyl-containing neolignan natural product isolated fromMagnoliaplants, is an interesting bio-based resource which is shown to be useful as a monomer for the synthesis of poly(honokiol carbonate) (PHC).