Query: bio-based epoxides carbon dioxide

title: Carbon dioxide and vegetable oil for the synthesis of bio based polymer precursors
abstract: Although it is a thermodynamically and kinetically stable molecule, carbon dioxide can beconverted into five and six membered cyclic carbonates by coupling with epoxides or oxetanes, respectively, using appropriate catalysts. Cyclic carbonates are used as green solvents, electrolytes for Liion batteries or intermediates for the synthesis of polymers. However, the catalytic performance must be further enhanced in particular for the coupling of CO2 with epoxidized vegetable oils or oxetanes. In this context, we developed a new highly efficient bicomponent homogeneous organocatalyst composed of anammonium salt as the catalyst and fluorinated single or double hydrogen bond donors as co catalysts. First,a screening of onium based catalysts and hydrogen bond donors was performed. Performances of thecatalysts and optimization of the reaction was realized through detailed kinetics studies using in situ FTIR/Raman spectroscopy under pressure. We demonstrated that fluorinated alcohols showed unexpected co catalytic activity due to synergisms between the onium salt and fluorinated co catalysts enabling the fast and selective addition of CO2 on to model epoxides and epoxidized vegetable oils under solvent free and mild experimental conditions. The use of this powerful dual catalyst was then extended to the first organocatalytic coupling of CO2 with less reactive oxetanes to produce hydroxyl telechelic oligocarbonates that were used asprecursor of CO2 based polyurethanes by chain extension with a diisocyanate. In addition, a fine comprehension of the mechanisms was investigated by DFT calculations highlighting that the co catalytic performance of the onium salt/fluorinated alcohol binary catalyst arose from the strong stabilization of the intermediates and transitions states by hydrogen bonding. To date, through comparative studies, we evidenced that this new catalyst is one

title: Recent advances of "soft" bio polycarbonate plastics from carbon dioxide and renewable bio feedstocks via straightforward and innovative routes
abstract: As one of the main plastic resin types, polycarbonate based plastics play an important role in manufacturing and wide applications. However, with increasing awareness of environmental challenges related to petroleum based polycarbonates, demand for production of bio based polycarbonates from carbon dioxide (CO2) and renewable feedstocks has attracted significant attention in view of green chemistry and sustainable development. This present review highlights recent advances in the efficient conversion of CO2 and bio based feedstocks to value added bio based polycarbonates with attractive properties. Specifically, an emphasis has been put to renewable bio based feedstocks that provide bio based epoxides with long chains, resulting in "soft" bio polycarbonate materials via innovative and efficient synthetic pathways. These bio based feedstocks, including plant oils, industrial byproducts (crude glycerol) and pure fatty acids as the comparison, trigger new platform to fully take advantage of CO2 and agricultural or industrial byproducts to bio degradable polycarbonate plastics. But, some challenges regarding comparable mechanical properties and scale up do exist. A comprehensive overview of epoxide properties, synthetic mechanism, and state of the art of bio based polycarbonates from designed bio based feedstocks are discussed in details. Additionally, an outlook of further engineering consideration has been touched providing insights and forecasts for developing value added bio products from CO2 and bio based feedstocks.

title: Bimetallic scorpionate based helical organoaluminum complexes for efficient carbon dioxide fixation into a variety of cyclic carbonates
abstract: A new family of bimetallic helical aluminum complexes can be obtained via warming up the preliminary dinuclear adduct complexes, or alternatively, by direct heating of the protioligands with 2 equiv. of AlR3. X ray diffraction analysis corroborated both the high coordination versatility in the ligands and the existence of helical chirality in the complexes. DFT calculations confirmed the preferential arrangement of the ancillary scorpionates in the bimetallic complexes and rationalized the proposed reaction mechanism. Bimetallic complexes were investigated as catalysts in combination with halides for the cycloaddition reaction of CO2 with a wide range of epoxides for cyclic carbonate formation. These studies led to the development of a sustainable, inexpensive, efficient and selective bicomponent system with a very broad substrate scope, including internal and challenging bio based trisubstituted terpene derived substrates, reaching high conversions for trans limonene oxide under mild conditions (79% conv. 70 degC, 10 bar CO2, 1 mol% 66 h)

title: An Efficient and Versatile Lanthanum Heteroscorpionate Catalyst for Carbon Dioxide Fixation into Cyclic Carbonates.
abstract: A new lanthanum heteroscorpionate complex has shown exceptional catalytic activity for the synthesis of cyclic carbonates from epoxides and carbon dioxide. This catalyst system also promotes the reaction of bio based epoxides to give an important class of bis(cyclic carbonates) that can be further used for the production of bio derived non isocyanate polyurethanes. The catalytic process requires low catalyst loading and mild reaction conditions for the synthesis of a wide range of cyclic carbonates.

title: Synthesis and thermal degradation kinetics of new terpolymer of carbon dioxide, cyclohexene oxide and alpha pinene oxide
abstract: Bio based polycarbonate, which was synthesized by terpolymerization of carbon dioxide (CO 2 and epoxides from natural resources, is attractive development direction in polymer fields. Bio based polycarbonate, however, is difficult to synthesize, and it's also accompanied by inferior thermal properties. In this study, a novel terpolymer was synthesized easily by the terpolymerization of CO 2 cyclohexene oxide (CHO) and alpha pinene oxide using homogeneous SalenCr III Cl as catalyst, and alpha pinene derived from abundant and natural pinene. Compared to the copolymer (PCHC) formed by copolymerization of CO 2 and CHO, the data of GPC shows that the terpolymer has relatively higher average molecular weight with 1.04 x 10 4 g/mol and narrower polydispersity (PDI) with 1.27. The thermal stability and thermal degradation of the terpolymer were deeply investigated, and the results proved that the terpolymer exhibits excellent thermal properties, and it has different thermal degradation mechanism compared with PCHC.

title: Recent advances in the use of catalysts based on natural products for the conversion of CO2into cyclic carbonates
abstract: The cycloaddition of carbon dioxide to epoxides is an efficient and clean method to obtain cyclic carbonates, which are used as green solvents, as electrolytes for lithium batteries and as intermediates for the synthesis of polymers and chemicals. This reaction requires a catalyst to overcome the low reactivity of carbon dioxide. The best catalysts for this transformation include a Lewis acid or hydrogen bond donor to activate the epoxide and a Lewis base as a nucleophile to open the ring of the oxirane cycle. The most commonly used catalysts are alkali halides, ammonium and phosphonium salts, which are organocatalysts containing hydrogen bond donor groups and metal based systems. To increase the sustainability and decrease the toxicity of the catalytic systems, many bio based products derived from natural sources have been used as catalysts or in combination with catalytic materials. The high functionality of natural products that contain amino and/or hydroxyl groups is used to activate an epoxide or reversibly capture carbon dioxide when used directly. But these products can also behave as auxiliaries, for instance, as ligands in metal based complexes, as biopolymer active supports for catalysts, as components for the skeleton of metal organic frameworks or to form ionic liquids or as deep eutectic solvents serving as an active medium for catalytic reactions. In this literature review, we present a structured overview of the reported chemical catalytic systems containing any component derived from a natural product. We discuss the amino acid based systems, cellulose, saccharides, lignin and lignocellulosic materials, choline derived species, guanidine and guanidinium salts, and other less explored compounds. Special emphasis has been placed on mechanistic studies providing information about the role of each component in these multifunctional systems.

title: The reactions of dimethyl carbonate and its derivatives
abstract: The worldwide urge to embrace a sustainable and bio compatible chemistry has led industry and academia to develop of chlorine free methodologies focused on the use of CO2 and CO2 based compounds as feedstocks, promoters and reaction media. In this scenario, dialkyl carbonates (DACs) and in particular dimethyl carbonate (DMC) occupy a privileged position due to their low toxicity, high biodegradability and peculiar reactivity. Nowadays, the large scale production of DACs is carried out through clean processes (i.e. phosgene free processes) which include the direct insertion of CO2 into epoxides, allowing in principle recycling of the carbon dioxide emitted during carbonate degradation. This groundbreaking achievement has definitely drawn attention toward the conception of procedures to activate the rather stable DACs with the aim of employing these compounds as green alternatives to their reactive chlorinated analogues. DACs are ambident electrophiles, which under appropriate conditions can undergo BAc2 or BAl2 nucleophilic substitution to give, respectively, alkoxycarbonylation and alkylation reactions. The many efforts devoted to improving the industrial suitability of organic carbonates have unveiled an intriguing and innovative chemistry as demonstrated by the numerous publications and patents published on these compounds over the last thirty years. This review reports on DACs as alkoxycarbonylating agents and their applications in industry and fine synthesis, as well as alkylating agents including allylic alkylation using palladium catalysts and the Pd/Ti bimetallic system and anchimerically driven alkylations via mustard carbonates. Moreover, the reactivity of organic carbonates toward several substrates and under different reaction conditions is described along with some distinctive DAC mediated cyclization and transposition reactions. The synthesis of olefins and ethers under both liquid and gas phase conditions via thermal decarboxylation of organic carbonates is also reported.

title: Potassium iodide polyethylene glycol catalyzed cycloaddition reaction of epoxidized soybean oil fatty acid methyl esters with CO2
abstract: Nowadays, the clean production of bio based products and fixation of carbon dioxide (CO2) are highly desirable. In this work, carbonated fatty acid methyl esters have been successfully prepared in 99% yield by cycloaddition of CO2 with bio based epoxidized methyl soyates. This was accomplished with a simple and cheap catalyst system of polyethylene glycol 400 (PEG 400) and potassium iodide (KI) under solvent free conditions. Experimental parameters such as the molar ratio of polyethylene glycol to metal halide, catalyst loading, reaction temperature, reaction time and CO2 pressure were systematically evaluated. The PEG 400 and KI co catalysts (4 mol% could significantly promote the cycloaddition of CO2 with internal epoxides (epoxidized methyl soyates) to produce carbonated fatty acid methyl esters. FT IR and NMR analyses were used to confirm the product, and 99% yield of the five membered cyclic carbonated methyl soyates was obtained at 120 degC with 3.0 MPa pressure of CO2 for 20 h. This method provides a cleaner approach for the production of bio based products.

title: polyethylene glycol catalyzed cycloaddition reaction of epoxidized soybean oil fatty acid methyl esters with CO 2
abstract: Nowadays, the clean production of bio based products and fixation of carbon dioxide (CO2) are highly desirable. In this work, carbonated fatty acid methyl esters have been successfully prepared in 99% yield by cycloaddition of CO2 with bio based epoxidized methyl soyates. This was accomplished with a simple and cheap catalyst system of polyethylene glycol 400 (PEG 400) and potassium iodide (KI) under solvent free conditions. Experimental parameters such as the molar ratio of polyethylene glycol to metal halide, catalyst loading, reaction temperature, reaction time and CO2 pressure were systematically evaluated. The PEG 400 and KI co catalysts (4 mol% could significantly promote the cycloaddition of CO2 with internal epoxides (epoxidized methyl soyates) to produce carbonated fatty acid methyl esters. FT IR and NMR analyses were used to confirm the product, and 99% yield of the five membered cyclic carbonated methyl soyates was obtained at 120 C with 3.0 MPa pressure of CO2 for 20 h. This method provides a cleaner approach for the production of bio based products.

title: High elasticity, chemically recyclable, thermoplastics from bio based monomers: carbon dioxide, limonene oxide and e decalactone
abstract: One solution to problems with petroleum derived plastics is to design polymers for the circular economy. In this regard, polymer chemistries, like ester or carbonate linkages, which are closer to equilibrium are very promising but to use these materials requires improvements to their properties and methods of manufacture. Here, efficient polymerization catalyses are used to transform wastes and bio sourced monomers into thermoplastics which combine high elasticity and strength and which can be degraded to allow for some chemical recycling. The plastics are prepared from carbon dioxide, limonene oxide (from waste citrus fruit peel) and e decalactone (from triglycerides) These monomers are polymerized, using catalyzed controlled polymerizations with high conversion efficiencies, to selectively form ABA block polymers (A high Tg polycarbonate, B low Tg polyester) The series of 5 poly(limonene carbonate) b poly(e decalactone) b poly(limonene carbonate) (PLC PDL PLC) samples allow for systematic variations in the overall molar masses (Mn 50 100 kg mol 1) and hard block compositions (21 63 wt% PLC) All the polymers are fully characterized using a range of spectroscopies, gel permeation chromatography, thermal and tensile mechanical measurements. The leading plastic combines tensile strength (stress at break, sb 21.2 MPa, Young's Modulus, Ey 321 MPa) and high elasticity (elongation at break, eb 400% an enhancement of more than 20x in elongation at break and tensile toughness over poly(limonene carbonate) overcoming the well known brittleness and processing limitations of PLC. It undergoes selective, catalyzed depolymerization to limonene oxide, carbon dioxide and the precursor polyester providing a future chemical recycling and upcycling opportunity.