13818-44-5Relevant articles and documents
Synthesis of cyclic carbonates from carbon dioxide and epoxides catalyzed by a keggin-type polyoxometalate-supported rhenium carbonyl derivate in ionic liquid
Huo, Zhiyuan,Zhao, Juan,Bu, Zhanwei,Ma, Pengtao,Liu, Qisen,Niu, Jingyang,Wang, Jingping
, p. 3096 - 3100 (2014)
A monovacant Keggin-type polyoxometalate-supported trirhenium carbonyl derivate [(CH3)4N]5H23[(PW11O39){Re(CO)3}3(μ3-O)(μ2-OH)]4·24H2O was synthesized. It was used as a catalyst for the synthesis of cyclic carbonates from carbon dioxide and epoxides under mild reaction conditions with co-catalyst pyrrolidinium bromide. The catalyst system was recycled 10 times with only a small decline in yield. The catalytic mechanism was hypothesized based on experimental results and the frontier orbitals computed by DFT calculations.
Triazine-based Organic Polymer-catalysed Conversion of Epoxide to Cyclic Carbonate under Ambient CO2 Pressure
Biswas, Tanmoy,Halder, Arjun,Paliwal, Khusboo S.,Mitra, Antarip,Tudu, Gouri,Banerjee, Rahul,Mahalingam, Venkataramanan
, p. 1683 - 1687 (2020)
In this work we have achieved epoxide to cyclic carbonate conversion using a metal-free polymeric catalyst under ambient CO2 pressure (1.02 atm) using a balloon setup. The triazine containing polymer (CYA-ANIS) was prepared from cyanuric chloride (CYA?Cl) and o-dianisidine (ANIS) in anhydrous DMF as solvent by refluxing under the N2 gas environment. The presence of triazine and amine functional groups in the polymer results in the adsorption of CO2 up to 7 cc/g at 273 K. This inspired us to utilize the polymer for the conversion of a series of functionalised epoxides into their corresponding cyclic carbonates in the presence of tetrabutyl ammonium iodide (TBAI) as co-catalyst. The product has wide range of applications like solvent in lithium ion battery, precursor for polycarbonate, etc. The catalyst was efficient for the conversion of different mono and di-epoxides into their corresponding cyclic carbonates under atmospheric pressure in the presence of TBAI as co-catalyst. The study indicates that epoxide attached with electron withdrawing groups (like, CH2Cl, glycidyl ether, etc.) displayed better conversion compared to simple alkane chain attached epoxides. This is mainly due to the stabilization of electron rich intermediates produced during the reaction (e. g. epoxide ring opening or CO2 incorporation into the halo-alkoxide anion). This catalyst mixture was capable to maintain its reactivity up to five cycles without losing its activity. Post catalytic characterization clearly supports the heterogeneous and recyclable nature of the catalyst.
New iron pyridylamino-bis(Phenolate) catalyst for converting CO2 into cyclic carbonates and cross-linked polycarbonates
Taherimehr, Masoumeh,Sert?, Jo?o Paulo Cardoso Costa,Kleij, Arjan W.,Whiteoak, Christopher J.,Pescarmona, Paolo P.
, p. 1034 - 1042 (2015)
The atom-efficient reaction of CO2 with a variety of epoxides has been efficiently achieved employing iron pyridylamino-bis(phenolate) complexes as bifunctional catalysts. The addition of a Lewis base co-catalyst allowed significant reduction in the amount of iron complex needed to achieve high epoxide conversions. The possibility of controlling the selectivity of the reaction towards either cyclic carbonate or polycarbonate was evaluated. An efficient switch in selectivity could be achieved when cyclic epoxides such as cyclohexene oxide and the seldom explored 1,2-epoxy-4-vinylcyclohexane were used as substrates. The obtained poly(vinylcyclohexene carbonate) presents pending vinyl groups, which allowed post-synthetic cross-linking by reaction with 1,3-propanedithiol. The cross-linked polycarbonate displayed a substantial increase in the glass transition temperature and chemical resistance, thus opening new opportunities for the application of these green polymers. CO2 meets epoxides: Iron pyridylamino-bis(phenolate) complexes are highly active catalysts for the atom-efficient reaction of CO2 with a variety of epoxides. The selectivity can be switched between the cyclic or polymeric carbonate when using cyclic epoxides such as cyclohexene oxide and 1,2-epoxy-4-vinylcyclohexaneas substrates. Cross-linking of the obtained poly(vinylcyclohexene carbonate) leads to substantial increase in the Tg and chemical resistance of the polymer.
Anion-induced 3d-4f luminescent coordination clusters: Structural characteristics and chemical fixation of CO2 under mild conditions
Zhang, Ruilian,Wang, Li,Xu, Cong,Yang, Huan,Chen, Wanmin,Gao, Guoshu,Liu, Weisheng
, p. 7159 - 7165 (2018)
Two series of anion-induced 3d-4f luminescent clusters ZnII2LnIII2L4 (LnIII = Eu3+, Tb3+, Er3+, Yb3+, Nd3+) and ZnII4LnIII2L4 (LnIII = Tb3+, Nd3+) based on μ3-OH group were synthesized and characterized. The difference in anions not only leads to significant structural changes, but also changes the luminescent properties of the 3d-4f coordination clusters. These complexes show excellent catalytic performance for CO2 conversion to obtain cyclic carbonates with wide substrate scopes and high selectivity under mild conditions. Turnover numbers were up to 9000, and turnover frequencies obtained were 660 h-1. The ligand is simple and the complexes are easily obtained even on a large scale. Moreover, these complexes also feature lanthanide-characterized luminescence both in visible and near infrared regions with relatively long luminescence lifetimes and high quantum yields, suggesting promising multifunctional applications.
Bifunctional one-component catalysts for the addition of carbon dioxide to epoxides
Büttner, Hendrik,Lau, Kornelia,Spannenberg, Anke,Werner, Thomas
, p. 459 - 467 (2015)
Several bifunctional ammonium salts were synthesized and employed as one-component catalysts for the conversion of CO2 and epoxides to produce cyclic carbonates. These catalysts show superior activities compared to their monofunctional analogs. A turnover number of up to 693 and a turnover frequency of up 392h-1 could be achieved for the best catalyst. Moreover, the effect of various solvents has been studied. All employed solvents and the product formed had a negative influence on substrate conversion. The scope and limitation of the reaction has been studied carefully for two general reaction protocols at 45 and 90-°C. In over 20 examples, the isolated yields after filtration were 90-%. In addition, we present the first organocatalyzed synthesis of a cyclohexene-based naturally occurring cyclic carbonate, and its molecular structure was determined by XRD. Furthermore, we demonstrate that the reaction can be performed even on a multigram scale and can be monitored by insitu FTIR spectroscopy. Couple up: Recyclable bifunctional ammonium salts are identified as one-component catalysts for the 100-% atom-economic coupling reaction of CO2 and epoxides even at 45-°C. The alcohol moiety that donates a hydrogen bond accelerates the catalytic reaction remarkably. This metal and solvent-free process can be performed on a multigram scale and is applied to the synthesis of a naturally occurring cyclic carbonate.
Simultaneous shaping and confinement of metal-organic polyhedra in alginate-SiO2spheres
Zhang, Zhuxiu,Lei, Yifan,Zhou, Jie,Cui, Mifen,Chen, Xian,Fei, Zhaoyang,Liu, Qing,Tang, Jihai,Qiao, Xu
, p. 14833 - 14836 (2020)
The simultaneous shaping and confinement of Cu-based MOP in alginate-SiO2 spheres significantly enhance the mechanical strength and leaching resistance of Cu-MOP. The resulting MOP-alginate-SiO2 is shown through chemical fixation of CO2 to exhibit improved product yield over the parent Cu-MOP and Cu-alginate-SiO2. This journal is
Transparent, flexible and highly conductive ion gels from ionic liquid compatible cyclic carbonate network
Jana, Satyasankar,Parthiban, Anbanandam,Chai, Christina L. L.
, p. 1488 - 1490 (2010)
Transparent, flexible, self-standing and highly ion conductive ion gels have been synthesised from novel ionic liquid compatible cyclic carbonate (CC) network polymer. The use of dual functional cyclic carbonate methacrylate (CCMA) monomer for the synthes
Highly Efficient Polymer-Supported Catalytic System for the Valorization of Carbon Dioxide
Desens, Willi,Kohrt, Christina,Frank, Marcus,Werner, Thomas
, p. 3815 - 3822 (2015)
Polydibenzo-18-crown-6 was utilized as a co-catalyst and polymeric support in combination with potassium iodide for the synthesis of cyclic carbonates from carbon dioxide and epoxides under mild and solvent-free conditions. The efficiency of this catalytic system can be easily increased by loading the polymer with KI prior to the reaction. The influence of various reaction parameters were studied thoroughly. The scope and limitation of the catalyst system was studied at 80 °C and 100 °C. A large number of terminal epoxides (14) were converted to the desired cyclic carbonates in yields up to 99 %. We could successfully recover and reuse the catalyst >20 times with excellent yields up to 99 %. Although, we observed that the activity gradually decreased after repetitive cycles. This decrease was attributed to KI leaching and partial degradation caused by mechanical stirring. This assumption is supported by scanning electron microscopy and energy dispersive X-ray spectroscopy.
Synthesis of bifunctional cyclic carbonates from CO2 catalysed by choline-based systems
Amaral, Adérito J.R.,Coelho, Jorge F.J.,Serra, Arménio C.
, p. 5518 - 5522 (2013)
Easily prepared choline iodide is an active catalyst for the synthesis of cyclic carbonates through the coupling reaction of CO2 and epoxides using low pressure (1 MPa), moderate temperature (85 °C) and green solvents (ethanol and propan-2-ol). The effects of reaction temperature, pressure, reaction time and amount of catalyst used were also investigated. The results showed moderate to high yields and excellent selectivities of cyclic carbonates with vinyl or acrylate groups under mild reaction conditions. The heterogenization of choline over a Merrifield resin gives access to a supported catalyst with good recyclability and reactivity that can be extended to a variety of terminal epoxide substrates.
An Efficient and Versatile Lanthanum Heteroscorpionate Catalyst for Carbon Dioxide Fixation into Cyclic Carbonates
Martínez, Javier,Fernández-Baeza, Juan,Sánchez-Barba, Luis F.,Castro-Osma, José A.,Lara-Sánchez, Agustín,Otero, Antonio
, p. 2886 - 2890 (2017)
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.
