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Processes 2020, 8, 548 11 of 22 must be applied under the conditions of high temperature and high pressure or in the presence of a solvent and/or co-catalyst. 3.2.1. Supported Catalyst A wide range of heterogeneous catalysts have been created, with the active sites being immobilized on various types of support, for example, ionic liquid grafted on polymer matrix [35,36], imidazolium derivatives functionalized on MCM-41 (Mobil Composition of Matter No. 41) silica-based materials [37], or triazolium-based ionic liquids on SBA-15 (Santa Barbara Amorphous-15) [38]. Normally, the covelent immobilization/functionalization is robust and can prevent the leaching of active species from the support. Supported Ionic Liquid Han et al. [39] synthesized highly cross-linked poly(N-vinylimidazole-co-divinylbenzene) (PVIm) beads with grafted ILs. By varying molar ratio of divinylbenzene to N-vinylimidazole, various pore sizes could be obtained and the highest IL immobilization of 0.92 mmol/g could be achieved. This study used several alkyl halides that covalently anchored on the PVIm surfaces to obtain variation of ILs-grafted porous polymer beads (PVIm2-RX). However, the author extensively studied PVIm grafted with N-butyl bromide (BuBr) by varied reaction parameters. The effect of temperature (90, 100, and 110 ◦C) on conversion of allyl glycidyl ether (AGE) showed increasing conversion of 49%, 60%, and 65%, respectively (Table 2). For the effect of pressures on catalytic activity at pressures of 8.6, 13.4, 16.2, and 18.2 bar, AGE conversion increased to 65%, 855, 94%, and 98%, respectively. PVIm-BuBr exhibited a good reusability with almost constant yield for five consecutive runs. Table 2. Supported catalysts for cycloaddition of CO2 to epoxides. Epoxide Catalyst Cocatalyst T P (◦C) (bar) 90 8.6 100 8.6 110 8.6 110 13.4 110 16.2 110 18.2 Time Yield Conv. (h) (%) (%) 6 48.02 49 6 58.8 60 6 64.35 65 6 84.15 85 6 93.06 94 6 97.02 98 Reusability Ref. 5 times, drop slightly after [39] fourth run 100%, 94%, 74%, 70% [40] 79%, 71%, 67%, 64% - [41] - - - [42] - - AGE PVIm2-BuBr - - - - - - SO ECH Bimetallic salen-merrifield resin - (single TBAB) Bimetallic salen-merrifield resin - (four TBAB) Bimetallic salen-silica 26 1 20100- 26 1 2079- 26 1 2486- - salen-aluminium pillared - supported(R = t-butyl) Bimetallic clay (R = t-butyl) MgFeAl-LDH TBAB TBAB TBAB - 26 1 24 25 5 48 50 1 7 50 5 7 50 5 7 50 5 7 21 - 92.83 96.3 74.28 75.8 96.04 98.0 7.39 7.6 16.6 17.0 - - Supported Bimetal–Organic Salen Complexes Although homogeneous catalysts such as Co(III) and Al(III) salen complexes show an effective catalytic system, it displays poor separation and low recyclability [17]. Thus, North et al. [40] attemptedPDF Image | Green Pathway Utilizing CO2 Cycloaddition Reaction Epoxide
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