Catalysis and polymer networks — the role of morphology and molecular accessibility

Corain, Benedetto; Zecca, Marco; Jeřábek, Karel

doi:10.1016/s1381-1169(01)00305-3

Cited by 123 publications

(87 citation statements)

References 98 publications

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“…the ion-exchanger, as the stationary phase in a liquid chromatography column, and measures elution volumes of solutes with a characteristic molecular size. Then, under the considered assumptions: (a) a simple geometric model can describe the pore system, and (b) the pore system can be treated as a discrete set of fractions with simple pores of a single size, the mathematical treatment of the data provided by the ISEC analysis provides information on pore volume distributions [6,7,32].…”

Section: Fig2 Isec Morphological Pattern Of the Gel-phasementioning

confidence: 99%

“…These processes take place mainly within the swollen polymer, or gel-like phase [2]. It is then of common sense Transesterification of triacetin with methanol on solid acid and base catalysts trying to correlate the catalytic performance of a resin with its swollen-state morphology, as well as with its functionalization degree.…”

Section: Relations Between Swollen-state Morphology and Catalytic Actmentioning

confidence: 99%

“…Gel-type ionexchangers consist in resins without an appreciable porosity in the dry state, whose interior is accessible only after swelling due to the reaction environment. Macroreticular resins count with agglomerates of gel-type zones, with their respective micropores, that form permanent macropores between them [2].…”

Section: Introductionmentioning

confidence: 99%

“…Regarding the process of functionalization in the resin manufacture, the simplest reaction is the direct sulfonation of polystyrene with concentrated sulfuric acid that gives the ion-exchangers known since the 1950s, though other functional groups can be introduced upon starting from lithiated or chloromethylated polystyrenes [2].…”

Section: Introductionmentioning

confidence: 99%

“…As it is known, certain properties of a reaction medium, such as polarity, have been marked to be strongly related to the swelling of the catalysts, allowing a higher accessibility of reactants to the functional groups and, thus, influencing the catalytic activity. Furthermore, the polarity of a reaction medium may vary throughout a reactive process and so would do the catalyst swelling [2,4,5].…”

Section: Introductionmentioning

confidence: 99%

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Catalytic Activity and Accessibility of Acidic Ion-Exchange Resins in Liquid Phase Etherification Reactions

et al. 2015

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Although macroreticular acidic ion-exchange resins have been widely used as catalysts in the industrial world for decades, their catalytic behavior is still far from being completely understood at a molecular level. Several characterization techniques coexist, which provide information about their properties. Only few of these techniques give an actual picture of their working-state features when swollen in anhydrous polar reactive media such as in etherification processes, where they are extensively used. The inverse steric exclusion chromatography technique, based on modeling the micropores structure, or gel-phase, as a set of discrete volume fractions with a characteristic polymer chain density, constitutes an appropriate procedure to assess the morphology of ion-exchangers in the swollen state. Present work proposes an empirical model to correlate the properties of the volume fractions with their catalytic activity in the etherification reaction rates of isobutene by addition of C1 to C4 linear primary alcohols. Sixteen different macroreticular acidic ion-exchange catalysts, both commercial and lab-made, have been used, which differ in acid capacity, sulfonation type, cross-linking degree and swollen-phase volume fractions distribution. Experimental reaction rates have been expressed as a sum of contributions of each individual volume fraction. The contribution of each polymer volume fraction corresponds to the product of the catalyst acidity, the characteristic volume fraction within the gel-phase of the catalyst, and a specific turnover frequency (TOF) of that fraction. Accessibility of the reacting alcohol, expressed in terms of the Ogston coefficient, has been also included in the empirical dependency equation presented in this work.

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Section: Fig2 Isec Morphological Pattern Of the Gel-phasementioning

confidence: 99%

Section: Relations Between Swollen-state Morphology and Catalytic Actmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Catalytic Activity and Accessibility of Acidic Ion-Exchange Resins in Liquid Phase Etherification Reactions

et al. 2015

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Highly Chemoselective Hydrogenation of 2-Ethylanthraquinone to 2-Ethylanthrahydroquinone Catalyzed by Palladium Metal Dispersed inside Highly Lipophilic Functional Resins

et al. 2002

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Catalysis by Ion‐Exchange Resins

Gates

2008

Handbook of Heterogeneous Catalysis

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The sections in this article are Introduction Classes of Ion‐Exchange Resin Catalysts: The Importance of Porosity Examples of Industrial Catalysis by Ion‐Exchange Resins Synthesis of Ion‐Exchange Resins Structure, Influence of Water, and Acidity in Ion‐Exchange Resins Accessibility, Swelling, and Mass Transfer Effects Mechanisms of Reactions Catalyzed by Sulfonic Acid Resins Kinetics of Reactions Catalyzed by Ion‐Exchange Resins Deactivation and Stability of Ion‐Exchange Resin Catalysts Modified and Metal‐Containing Ion‐Exchange Resin Catalysts Hybrid Organic/Inorganic Catalysts akin to Ion‐Exchange Resins Summary and Outlook Acknowledgments

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Catalysis and polymer networks — the role of morphology and molecular accessibility

Cited by 123 publications

References 98 publications

Catalytic Activity and Accessibility of Acidic Ion-Exchange Resins in Liquid Phase Etherification Reactions

Catalytic Activity and Accessibility of Acidic Ion-Exchange Resins in Liquid Phase Etherification Reactions

Highly Chemoselective Hydrogenation of 2-Ethylanthraquinone to 2-Ethylanthrahydroquinone Catalyzed by Palladium Metal Dispersed inside Highly Lipophilic Functional Resins

Catalysis by Ion‐Exchange Resins

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