Synthesis of isosorbide-based polycarbonates via melt polycondensation catalyzed by quaternary ammonium ionic liquids

Sun, Wei; Xu, Fengyuan; Cheng, Weiguo; Sun, Jian; Gao, Ning; Zhang, Suojiang

doi:10.1016/s1872-2067(17)62822-5

Cited by 39 publications

(29 citation statements)

References 51 publications

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“…According to the experimental results, simulation results, and previous reports, a plausible nucleophilic activation mechanism was proposed (Scheme ). The oxygen atom of [4‐R‐Phen] − (R=H, F, Cl, Br, or I) was anticipated to facilitate the nucleophilic activation of isosorbide through a hydrogen bond, similarly to that mentioned in other literature . This deduction was verified by the 1 H NMR chemical shift of the mixture of isosorbide and [P 66614 ][4‐H‐Phen].…”

Section: Resultssupporting

confidence: 64%

Transesterification of Isosorbide with Dimethyl Carbonate Catalyzed by Task‐Specific Ionic Liquids

Qian

Tan

et al. 2019

ChemSusChem

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Green synthesis of high‐molecular‐weight isosorbide‐based polycarbonate (PIC) with excellent properties is a tremendous challenge and is profoundly influenced by the precursor. Herein, an ecofriendly catalyst was employed to obtain the more reactive PIC precursor dicarboxymethyl isosorbide (DC) with 99.0 % selectivity through the transesterification reaction of isosorbide with dimethyl carbonate. This is the indispensable stage of a one‐pot green synthesis of PIC, playing a critical role in giving an insight into the polymerization mechanism of polymer synthesis through the melt transesterification reaction. To this end, a series of 4‐substituted phenolate ionic liquids (ILs) were developed as a new type of high‐efficiency catalyst for this reaction. These homogeneous ILs exhibited outstanding catalytic performances. The DC selectivity increased gradually with decreasing IL basicity; among the ILs studied, trihexyl(tetradecyl)phosphonium 4‐iodophenolate ([P66614][4‐I‐Phen]) showed the highest catalytic activity. Additionally, according to the experimental results and DFT calculations, a plausible nucleophilic activation mechanism was proposed, which confirmed that the reaction is activated through the formation of H‐bonds and electrostatic interactions with the IL catalyst. This strategy of tunable basicity and structure of anions in ILs affords an opportunity to develop other ILs for the transesterification reaction, thereby conveniently providing a variety of polymers through a green synthetic pathway.

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Section: Resultssupporting

confidence: 64%

Transesterification of Isosorbide with Dimethyl Carbonate Catalyzed by Task‐Specific Ionic Liquids

Qian

Tan

et al. 2019

ChemSusChem

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“…Finally, we also chose the acidic anions to coordinate with Na + as catalyst for synthesis of PIC (Table , entries 10–12), and the experimental results showed that the conversion of ISB was generally low. Especially, the sodium formate showed a little activity for this reaction, and almost no product was detected, which indicated that the acidity of catalyst was not conducive to the transesterification reaction, just like the other articles reported. ,, …”

Section: Resultsmentioning

confidence: 59%

“…Especially, the sodium formate showed a little activity for this reaction, and almost no product was detected, which indicated that the acidity of catalyst was not conducive to the transesterification reaction, just like the other articles reported. 20,36,43 Molecular Structure of Oligomer. The terminal groups of oligomers were investigated by 1 H NMR (Table 1).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…However, green synthesis of high-performance PIC remains a challenge. First, the low reactivity of the endohydroxyl (endo–OH) in the ISB molecule makes it difficult to synthesize PIC with a high molecular weight. , As shown in Scheme , ISB possesses two cis-connected tetrahydrofurans where exohydroxyl groups (exo–OH) and endo–OH are positioned outside and inside of the two cis-fused rings, respectively . Each hydroxyl group exhibits different reactivity.…”

Section: Introductionmentioning

confidence: 99%

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Cost-Effective Synthesis of High Molecular Weight Biobased Polycarbonate via Melt Polymerization of Isosorbide and Dimethyl Carbonate

Yang

Liu

et al. 2020

ACS Sustainable Chem. Eng.

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Green synthesis of poly(isosorbide carbonate) (PIC) with remarkable properties is a huge challenge in industrial applications due to low molecular weight and harsh reaction conditions. We reported a novel pathway to synthesize high molecular weight PIC through melt polymerization of isosorbide (ISB) and dimethyl carbonate (DMC), which are derived from the biomass and CO2, respectively. The effects of metal ion-containing compound catalyst on chemical structures, terminal groups, and molecular weight of PIC in the process of melt polycondensation were studied. Compared with the best reported catalyst lithium acetylacetonate, the weight-average molecular weight (M w) of PIC was increased by using our preferred catalyst sodium tert-butoxide from 46 500 to 55 100 with the ISB conversion up to 99.0%, and the reaction time was decreased from 12 h to only 2.5 h, as far as we know, which is the highest M w value and the most efficient catalyst achieved by one-step method. According to the results of the experiment and simulation, we found that high catalytic performance was ascribed to the weak interaction energy of anion–cation of catalyst and the strong proton acceptance ability of the anion of the catalyst. Meanwhile, increasing the interaction energy of anion–cation of the catalyst could inhibit the occurrence of the methylation side reaction and interestingly the activated endohydroxyl groups of ISB were found to be more easily methylated. Finally, based on the captured and detected intermediates of the two-stages of the reaction, a possible mechanim for the synergetic effects of cation–anion through hydrogen bond formation was proposed.

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“…In this regard, a large range of catalysts was tested to selectively activate the endo or exo alcohol moieties and to prevent reactivity disparities that would considerably limit the molar mass of the PC. Among them, metal salts [202], metal alkoxides [203,204], inorganic carbonates [205], ionic liquids [206][207][208][209][210][211][212][213], organic bases [214] and others [215][216][217][218] enabled the facile construction of defect-free PCs derived from isosorbide with Mn values in the range of 14,000 to 55,000 g/mol. Carbonate metathesis polymerization principle catalyzed by K 2 CO 3 .…”

Section: Aromatic and Cycloaliphatic Pcsmentioning

confidence: 99%

En Route to CO2-Based (a)Cyclic Carbonates and Polycarbonates from Alcohols Substrates by Direct and Indirect Approaches

et al. 2022

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This review is dedicated to the state-of-the art routes used for the synthesis of CO2-based (a)cyclic carbonates and polycarbonates from alcohol substrates, with an emphasis on their respective main advantages and limitations. The first section reviews the synthesis of organic carbonates such as dialkyl carbonates or cyclic carbonates from the carbonation of alcohols. Many different synthetic strategies have been reported (dehydrative condensation, the alkylation route, the “leaving group” strategy, the carbodiimide route, the protected alcohols route, etc.) with various substrates (mono-alcohols, diols, allyl alcohols, halohydrins, propargylic alcohols, etc.). The second section reviews the formation of polycarbonates via the direct copolymerization of CO2 with diols, as well as the ring-opening polymerization route. Finally, polycondensation processes involving CO2-based dimethyl and diphenyl carbonates with aliphatic and aromatic diols are described.

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Synthesis of isosorbide-based polycarbonates via melt polycondensation catalyzed by quaternary ammonium ionic liquids

Cited by 39 publications

References 51 publications

Transesterification of Isosorbide with Dimethyl Carbonate Catalyzed by Task‐Specific Ionic Liquids

Transesterification of Isosorbide with Dimethyl Carbonate Catalyzed by Task‐Specific Ionic Liquids

Cost-Effective Synthesis of High Molecular Weight Biobased Polycarbonate via Melt Polymerization of Isosorbide and Dimethyl Carbonate

En Route to CO2-Based (a)Cyclic Carbonates and Polycarbonates from Alcohols Substrates by Direct and Indirect Approaches

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