CO2-catalysed carbamation of aminofunctional silanes

Aresta, Michele; Quaranta, Eugenio; Dibenedetto, Angela; Tommasi, Immacolata; Marciniec, Bogdan

doi:10.1002/1099-0739(200012)14:12<871::aid-aoc93>3.0.co;2-h

Cited by 55 publications

(88 citation statements)

References 7 publications

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“…1 Carbon dioxide might also be utilized as an oxygen source or oxidant because it can be considered a nontraditional or mild oxidant and oxygen transfer agent. 2,3 It has been recently reported that carbon dioxide can be utilized as an oxidant for the oxidative conversions of alkanes, alkenes, and alcohols 4 and that oxygen generated during CO 2 reduction can participate in both partial oxidation and dehydrogenation. 4,5 Catalytic dehydrogenation of ethylbenzene (EB) is important in the manufacture of a styrene monomer (SM), which needs a large excess amount of superheated steam for preventing catalyst deactivation due to coke formation as well as enhancing catalytic activity.…”

Section: Introductionmentioning

confidence: 99%

CO2 utilization for the formation of styrene from ethylbenzene over zirconia-supported iron oxide catalysts

Noh

Chang

Park

et al. 2000

Appl. Organometal. Chem.

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Dehydrogenation of ethylbenzene with carbon dioxide has been carried out over zirconia-based catalysts. Carbon dioxide in this reaction was found to play a beneficial role as an oxidant for promoting catalytic activity. The addition of a ceria promoter to zirconia improved the catalytic activity significantly, which was attributed to increasing basicity as well as oxygen vancancies. The loading of iron oxide onto only zirconia among zirconia-related materials is effective for improving the activity.

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Section: Introductionmentioning

confidence: 99%

CO2 utilization for the formation of styrene from ethylbenzene over zirconia-supported iron oxide catalysts

Noh

Chang

Park

et al. 2000

Appl. Organometal. Chem.

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“…7 Conversely, when unsaturated rhodium (I) complexes 'Rh(L-L)Cl' bearing a bidentate ligand (L-L = diphosphine, dipyridyl) are used, the mechanism of deactivation follows a different pathway. In this case, the coordinatively unsaturated 'Rh(L-L)Cl' moiety can be converted, by reaction with olefins, into a mixture of the penta-coordinated rhodium complex, Rh(L-L) 2 Cl, which no longer shows catalytic properties, 7 and Rh(olefin) n Cl, which is inactive. Owing to these facts, the life time of the catalyst rarely exceeds a few hours, with a serious limitation on the potential application in synthetic chemistry.…”

Section: Resultsmentioning

confidence: 99%

Direct synthesis of organic carbonates by oxidative carboxylation of olefins catalyzed by metal oxides: developing green chemistry based on carbon dioxide

Aresta

Dibenedetto

Tommasi

2000

Appl. Organometal. Chem.

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In this paper we report on the 'oxidativecarboxylation' of olefins catalysed by either transition metal complexes or metal oxides. We discuss the oxidation mechanism under homogeneous and heterogeneous conditions. In the former case the process is driven by co-ordination to the metal centre, in the latter a radical reaction takes place. The yield of carbonate is strongly dependent on the catalyst used. Copyright #

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“…142 Interestingly, CO 2 catalyzes reaction of aminosiloxanes H 2 NC 3 H 6 Si(OR) 3 with dimethylcarbonate to yield methyl carbamate esters. 144 The sol-gel hydrolytic condensation of such carbamates synthesized from mono-and diaminosiloxanes occurs without the decomposition of the carbamates. 145,146 Thermal treatment releases CO 2 to provide aminosilica materials retaining initial lamellar structure.…”

Section: Non-aqueous Solutions Of Amine Absorbentsmentioning

confidence: 99%

Novel High Capacity Oligomers for Low Cost CO2 Capture

Perry¹,

Grocela-Rocha²,

O’Brien³

et al. 2010

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The novel concept of using a molecule possessing both physi-sorbing and chemi-sorbing properties for post-combustion CO2 capture was explored and mixtures of aminosilicones and hydroxyterminated polyethers had the best performance characteristics of materials examined. The optimal solvent composition was a 60/40 blend of GAP-1/TEG and a continuous bench-top absorption/desorption unit was constructed and operated. Plant and process models were developed for this new system based on an existing coal-fired power plant and data from the laboratory experiments were used to calculate an overall COE for a coal-fired power plant fitted with this capture technology. A reduction in energy penalty, from 30% to 18%, versus an optimized 30% MEA capture system was calculated with a concomitant COE decrease from 73% to 41% for the new aminosilicone solvent system. 3 Executive SummaryThe novel concept of using a molecule possessing both physi-sorbing and chemi-sorbing properties for post-combustion CO2 capture was explored. A variety of candidate materials with physi-sorbing backbones and chemically reactive peripheral groups were considered with the final selection primarily focusing on aminosilicones. A small effort was also devoted to derivatized plant oils.None of the plant oil derivatives were effective in absorbing CO2 in laboratory experiments. Model reactions suggest that both intra-molecular H-bonding between adjacent hydroxyl and amino groups and potential micelle formation suppressed reactions with CO2. This route was abandoned in favor of the aminosilicones.A variety of aminosilicones with differing architectures and type and placement of amine groups were examined both experimentally and computationally for physical properties as well as CO2 capture efficacy. Modeling indicated that the heat reaction of sterically hindered amines with CO2 was lower than for unhindered amines and that less basic amines also decreased the heat of reaction. This provided options to tune the heat of reaction for optimal plant performance. Physical property predictions were also made for viscosity, vapor pressure, density and CO2 solubility. Limited experimental data confirmed the accuracy of the density and solubility models as well as trend predictability in heats of reaction. However, viscosity predictions were not accurately modeled and vapor pressure data was unavailable.Synthetically, GEN 1 aminosilicone solvents with linear, branched, cyclic and star architectures were made that possessed mono and di-amine groups while other solvent candidates had varying degrees of steric hindrance. Oligomers as well as discrete small molecules were prepared and evaluated. These included solvents with covalently bound polyether units. CO2-capture experiments were performed using both high throughput screening (HTS) techniques as well as small-scale laboratory testing. Mass transfer issues prevented the HTS methodology from being as useful as anticipated. However, efficient mixing on the lab-scale provided reliable data. These experiment...

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CO2-catalysed carbamation of aminofunctional silanes

Cited by 55 publications

References 7 publications

CO2 utilization for the formation of styrene from ethylbenzene over zirconia-supported iron oxide catalysts

CO2 utilization for the formation of styrene from ethylbenzene over zirconia-supported iron oxide catalysts

Direct synthesis of organic carbonates by oxidative carboxylation of olefins catalyzed by metal oxides: developing green chemistry based on carbon dioxide

Novel High Capacity Oligomers for Low Cost CO2 Capture

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