2463-45-8Relevant articles and documents
CYCLIC CARBONATES OBTAINED BY REACTIONS OF ALKALI METAL CARBONATES WITH EPIHALOHYDRINS.
Rokicki,Kuran
, p. 1662 - 1666 (1984)
A study has been carried out on the reaction of alkali metal carbonates with epihalohydrins in the presence of cation complexing agents e. g. crown ethers. 3-Glycidyloxypropylene carbonate was found to be formed as the main product of the reaction of epichlorohydrin with potassium carbonate promoted by 18-crown-6. The effect of various epihalohydrins and alkali metal carbonates on the reaction course was examined. It was found that the reaction of potassium hydrogencarbonate with epichlorohydrin gives 4-hydroxymethyl-1,3-dioxolan-2-one. When the reaction of epihalohydrins with potassium carbonates was carried out in the atmosphere of carbon dioxide the products contained linear carbonate linkage apart from cyclic one.
A highly augmented, (12,3)-connected Zr-MOF containing hydrated coordination sites for the catalytic transformation of gaseous CO2 to cyclic carbonates
Jin, Guanghua,Sensharma, Debobroto,Zhu, Nianyong,Vaesen, Sebastien,Schmitt, Wolfgang
, p. 15487 - 15492 (2019)
A porous Zr-based MOF, [Zr6(BTEB)4(μ3-O)4(μ3-OH)4(H2O)4], which contains partially hydrated, 12-connected {Zr6} nodes and extended carboxylate ligands (BTEB3-), was synthesized and physicochemically characterised. The resulting (12,3)-connected, 3D framework adopts an uncommon llj topology with a large, solvent accessible void volume of ca. 79% of the unit cell volume. The porous structure facilitates the uptake of N2 and activated samples give rise to BET surface areas of >1000 m2 g-1. Furthermore, the porosity and accessibility of Lewis acidic Zr(iv) sites promote the catalytic transformation of gaseous CO2 to cyclic carbonates via cycloaddition reactions using epoxide reactants, whereby solvated MOFs exhibit higher catalytic performance than thermally treated samples.
-
De Pasquale
, p. 157 (1973)
-
A green catalysis of CO2 fixation to aliphatic cyclic carbonates by a new ionic liquid system
Wong, Wing-Leung,Lee, Lawrence Yoon Suk,Ho, Kam-Piu,Zhou, Zhong-Yuan,Fan, Ting,Lin, Zhenyang,Wong, Kwok-Yin
, p. 160 - 166 (2014)
A mixed ionic liquid system has been developed for the efficient catalysis of CO2 addition to aliphatic epoxides without involving any transition metal catalysts or other additives. The ionic liquid integrated with pyridinium and pyrrolidinium groups (1·(Br)3) together with a non-polar ionic liquid (3·(Ntf)2) effectively transformed non-polar aliphatic epoxides to cyclic carbonates by the reaction with CO 2 under mild CO2 pressure (3.0 MPa) and reaction temperature (80 C). The presence of 3·(Ntf)2 remarkably improved the catalytic activity of 1·(Br)3 towards non-polar epoxides by increasing the miscibility of catalyst with the substrates. The mixed ionic liquid system is robust enough to be recycled without any significant loss of catalytic activity. GC-MS studies were performed to reveal the reaction pathways to the cyclic carbonates and a feasible model accounting for the effective CO2 activation in the ionic liquid system was proposed using density functional theory (DFT) calculations.
In situconstruction of phenanthroline-based cationic radical porous hybrid polymers for metal-free heterogeneous catalysis
Chen, Guojian,Zhang, Yadong,Liu, Ke,Liu, Xiaoqing,Wu, Lei,Zhong, Hu,Dang, Xuejing,Tong, Minman,Long, Zhouyang
supporting information, p. 7556 - 7565 (2021/04/06)
Rational design of multifunctional radical porous polymers with redox activity for targeted metal-free heterogeneous catalysis is an important research topic. In this work, we reported a new class of phenanthroline-based cationic radical porous hybrid polymers (Phen˙+-PHPs), which were constructed from the Heck reaction between a newly designed dibromo-substituted phenanthroline ionic monomer (iDBPhen) and a rigid building block, octavinylsilsesquioxane (VPOSS). For the first time, the stable phenanthroline-based radical cation was unexpectedly discovered in these polyhedral oligomeric silsesquioxane (POSS)-based porous hybrid polymers, probably undergoingin situreduction of the dicationic monomer iDBPhen during the alkaline reagent K2CO3-involved Heck reaction. The radical characters of the typical porous polymers Phen˙+-PHP-2 and Phen˙+-PHP-2Br were confirmed from the electron paramagnetic resonance (EPR) spectra and X-ray photoelectron spectra (XPS). The chemical structures and porous geometry were fully characterized by a series of advanced technologies. Surprisingly, the metal-free cationic radical polymer Phen˙+-PHP-2 exhibited high heterogeneous catalytic efficiency in the H2O2-mediated selective oxidation of various sulfides to sulfoxides with high yields under mild conditions, owing to the electron-accepting and redox ability of Phen-based dications and radical cations. Moreover, the extended sample Phen˙+-PHP-2Br prepared by post-treatment of Phen˙+-PHP-2 with aqueous HBr was also employed as a metal-free efficient heterogeneous catalyst in the conversion of CO2with epoxides into cyclic carbonates under atmospheric pressure and low temperatures. The remarkable catalytic performance in CO2conversion should be assigned to the synergistic catalysis of POSS-derived Si-OH groups and nucleophilic Br?anions and N active atom-involved Phen cationic radical moieties within Phen˙+-PHP-2Br. These two catalysts can be facilely recovered and reused, also with stable recyclability in the above catalytic reaction systems, achieving the heterogeneous catalytic demands for multipurpose reactions.
Method for preparing cyclic carbonate through catalysis of hydrogen bond donor functionalized polymeric ionic liquid
-
Paragraph 0049-0087; 0093-0097, (2021/02/10)
The invention provides a preparation method of a hydrogen bond donor functionalized polymerization ionic liquid catalyst, and a method for synthesizing cyclic carbonate by catalyzing CO2 and epoxide with the catalyst. According to the method, an imidazolyl ionic liquid monomer and a hydrogen bond donor monomer are subjected to cross-linking polymerization in proportion to form the polymerized ionic liquid catalyst, the catalyst can efficiently catalyze CO2 and epoxide to be converted into cyclic carbonate under the optimal reaction condition, and the yield can reach 99%. Compared with a traditional catalyst, the polymerization ionic liquid catalyst has the advantages that a hydrogen bond donor and ionic liquid are effectively combined in a free radical polymerization manner to form a heterogeneous catalyst which has the advantages of rich hydrogen bond donor, dispersed active sites, good catalytic effect, simple preparation method, good cycle performance, simple separation and the like, and huge industrial application potential is achieved.
