Swelling Poly(ionic liquid)s: Synthesis and Application as Quasi-Homogeneous Catalysts in the Reaction of Ethylene Carbonate with Aniline

Zhang, Yongya; Wang, Binshen; Elageed, Elnazeer H. M.; Qin, Li; Ni, Bing; Liu, Xiuli; Gao, Guohua

doi:10.1021/acsmacrolett.6b00178

Cited by 71 publications

(67 citation statements)

References 40 publications

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“…Therefore, these swollen polymers could be considered as PIL‐based organogels and might provide a suitable microenvironment with enhanced catalytic performance during the chemical transformation of CO 2 . Similar inferences and interesting phenomena have also been reported by Gao et al., Ding et al., and others…”

Section: Resultssupporting

confidence: 91%

Charged Metalloporphyrin Polymers for Cooperative Synthesis of Cyclic Carbonates from CO₂ under Ambient Conditions

et al. 2017

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A facile and one-pot synthesis of metalloporphyrin-based ionic porous organic polymers (M-iPOPs) was performed through a typical Yamamoto-Ullmann coupling reaction for the first time. We used various characterization techniques to demonstrate that these strongly polar Al-based materials (Al-iPOP) possessed a relatively uniform microporosity, good swellable features, and a good CO capture capacity. If we consider the particular physicochemical properties, heterogeneous Al-iPOP, which bears both a metal active center and halogen anion, acted as a bifunctional catalyst for the solvent- and additive-free synthesis of cyclic carbonates from various epoxides and CO with an excellent activity and good recyclability under mild conditions. Interestingly, these CO -philic materials could catalyze the cycloaddition reaction smoothly by using simulated flue gas (15 % CO in N , v/v) as a raw material, which indicates that a stable local microenvironment and polymer swellability might promote the transformation. Thus, the introduction of polar ionic liquid units into metalloporphyrin-based porous materials is regarded as a promising new strategy for the chemical conversion of CO .

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Section: Resultssupporting

confidence: 91%

Charged Metalloporphyrin Polymers for Cooperative Synthesis of Cyclic Carbonates from CO₂ under Ambient Conditions

et al. 2017

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“…Notably, P[VBIM][OAc]‐10% exhibited an even better catalytic performance than homogeneous catalyst BmimOAc (87%) (entry 8). This implied that the swelling ratio of PILs had a great influence on their catalytic activities . With same number of active sites, the PILs with higher swelling ratio exhibited higher activities mainly due to the sufficient exposure of active sites to reactants.…”

Section: Resultsmentioning

confidence: 99%

“…The activity of anion decreased in order OAc − > Cl − ≈ Br − , which was in agreement with hydrogen bond basicity according to our previous reports,. P[VBIM][AA]‐10%, where the carboxylate group was connected to the polymer chain, gave a relatively lower yield (82%) than P[VBIM][OAc]‐10% (95%) (entry 7). This suggested that the mobility of catalytically active sites also played an important role in the reaction.…”

Section: Resultsmentioning

confidence: 99%

“…To solve this problem, the usual ways are to make nano and/or porous PILs, thus accelerating mass transfer and promoting dispersion and accessibility of active sites, leading to the dramatic promotion of catalytic activity . Very recently, our group first reported nonporous PIL beads with swelling property (namely swelling PILs) as high efficient catalysts, which was synthesized by simple free radical polymerization . The swelling PILs exhibited a similar activity to the homogeneous catalyst 1‐butyl‐3‐methyl‐imidazolium acetate (BmimOAc) in the reaction of aniline and ethylene carbonate (EC).…”

Section: Introductionmentioning

confidence: 99%

“…Therefore, a number of greener synthetic procedures have been developed to avoid the utilization of toxic phosgene and isocyanate . Our group has dedicated to the green synthesis of 3‐aryl‐2‐oxazolidinones catalyzed by ionic liquids over the last few years ,. We have reported approaches to synthesize oxazolidinones by the reactions of cyclic carbonates and aromatic amines,,– the straightforward conversion of CO 2 using epoxides and aromatic amines,– the direct condensation of 2‐(arylamino) alcohols with diethyl carbonate (DEC), and the cycloaddition reactions of epoxides with arylcarbamates …”

Section: Introductionmentioning

confidence: 99%

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Swelling Poly (Ionic Liquid)s: Heterogeneous Catalysts That are Superior than Homogeneous Catalyst for Ethylene Carbonate Transformation

Zhang

Chen

et al. 2017

ChemistrySelect

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Heterogeneous catalysts usually show much lower catalytic activities than homogeneous catalysts due to insufficient dispersion and contact of catalytically active sites to reactants. Efforts have been made to solve this problem during past decades. Herein, we have synthesized a series of poly (ionic liquid)s (PILs), which are well swelled in ethylene carbonate (EC), by polymerization of N‐vinylimidazolium ionic liquid monomers with divinylbenzene (DVB). The structure, morphology and swelling property of the PILs were charicreized by 13C MAS NMR, FT‐IR and SEM. Cyro‐SEM showed that the PILs demonstrate a 3D network structure in swelling state which might promote mass transfer and dispersion of active sites. The PILs were utilized in the reaction of 2‐(phenylamino) ethanol (2‐PAE) and EC and exhibited even better catalytic performance than homogeneous catalyst 1‐butyl‐3‐methyl‐imidazolium acetate (BmimOAc). This superior catalytic activity is strongly related to the swelling property and selective absorption behavior of PILs. The absorption behavior was investigated by 1H NMR analysis of mole ratio of reactants to product inside and outside of PILs in the reaction mixture. It was found that the PILs could enrich reactants and eject products which could accelerate the reaction.

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Thin‐Film Composite Polyionic Liquid Gel Membranes and Their Potential for Nanofiltration in Organic Solvents

Alkharabsheh

Bernstein

2018

Adv Materials Inter

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processes, [13][14][15][16] membrane modification, [17] and fabricating nanocomposite and mixed matrix membranes. [1,[18][19][20][21][22][23] Lately, research on SRNF membranes has focused on fabricating membranes from completely new materials such as graphene and other carbon materials, [24][25][26] metal hydroxides, [27] and metal-organic framework membranes, [28,29] or from new polymers. [30][31][32][33][34] One very promising group of materials for SRNF TFC membranes is polyelectrolyte (PE). PE-based SRNF membranes fabricated by layer-by-layer deposition or coating techniques [35][36][37] showed promising high selectivities, however, their permeabilities were low. [38] The low solubility of PEs in organic solvents due to charge condensation as well as thick active layers were probably the two main reasons for the low permeabilities. [39] Reducing the active layer thickness by decreasing the number of layers improved the permeability, but also reduced the selectivity. [38] Other approaches to increasing the permeability of PE-based membranes included incorporating graphene oxide nanosheets into the PE, [40] fabricating an ionically crosslinked asymmetric PE membrane, [41] using a weak PE [42] and a branched PE. [38] A promising new type of PE for fabricating SRNF TFC membranes which is yet to be explored is polymeric ionic liquids (PILs). PILs are solid, strong PEs that carry an ionic liquid species (cationic or anionic) constrained to the repeating units in the PE chain. [43] Unlike traditional PEs, in organic solvents PILs can swell and their counterion is delocalized, depending on the polymer and counterion types, mainly due to the hydrophobic character of the counterion and the reduced Coulombic interactions. [43,44] The swelling of the active layer in solvents is an important parameter that influences the membrane performance, that is, permeance and selectivity. [35] Low membrane permeance can be attributed to low swelling of the active layer, [45,46] but high swelling results in low selectivity or low membrane stability, [38,47,48] hence, the swelling degree of PILbased membranes must be restricted. This can be achieved by the addition of a cross-linker monomer (i.e., PIL gel) and by the choice of the PIL monomer and counterion. [49,50] Membrane permeance is also proportional to the active layer thickness: high permeability requires a thin active layer. [14,38] The selectivity of crosslinked PE-based nanofiltration membranes is proportional to the surface charge and the membrane molecular weight cutoff, namely, the cross-linker density. [35,38] The Polymeric ionic liquid (PIL) gels can serve as a promising material for the fabrication of solvent resistance nanofiltration (SRNF) membranes, given the solubility and the high delocalization of the counterion of PILs in organic solvents. This research describes the fabrication of a new thin-film composite membrane (TFC) with a crosslinked PIL (i.e., PIL gel) as an active layer and demonstrates its great potential as an SRNF membrane. A hydrophobic and positiv...

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Swelling Poly(ionic liquid)s: Synthesis and Application as Quasi-Homogeneous Catalysts in the Reaction of Ethylene Carbonate with Aniline

Cited by 71 publications

References 40 publications

Charged Metalloporphyrin Polymers for Cooperative Synthesis of Cyclic Carbonates from CO₂ under Ambient Conditions

Charged Metalloporphyrin Polymers for Cooperative Synthesis of Cyclic Carbonates from CO₂ under Ambient Conditions

Swelling Poly (Ionic Liquid)s: Heterogeneous Catalysts That are Superior than Homogeneous Catalyst for Ethylene Carbonate Transformation

Thin‐Film Composite Polyionic Liquid Gel Membranes and Their Potential for Nanofiltration in Organic Solvents

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Swelling Poly(ionic liquid)s: Synthesis and Application as Quasi-Homogeneous Catalysts in the Reaction of Ethylene Carbonate with Aniline

Cited by 71 publications

References 40 publications

Charged Metalloporphyrin Polymers for Cooperative Synthesis of Cyclic Carbonates from CO2 under Ambient Conditions

Charged Metalloporphyrin Polymers for Cooperative Synthesis of Cyclic Carbonates from CO2 under Ambient Conditions

Swelling Poly (Ionic Liquid)s: Heterogeneous Catalysts That are Superior than Homogeneous Catalyst for Ethylene Carbonate Transformation

Thin‐Film Composite Polyionic Liquid Gel Membranes and Their Potential for Nanofiltration in Organic Solvents

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Product

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Charged Metalloporphyrin Polymers for Cooperative Synthesis of Cyclic Carbonates from CO₂ under Ambient Conditions

Charged Metalloporphyrin Polymers for Cooperative Synthesis of Cyclic Carbonates from CO₂ under Ambient Conditions