Controlling desolvation through polymer-assisted grinding

Terban, Maxwell W.; Madhau, Leillah; Cruz‐Cabeza, Aurora J.; Okeyo, Peter Ouma; Etter, Martin; Schulz, Armin; Rantanen, Jukka; Dinnebiér, Robert E.; Billinge, Simon J. L.; Moneghini, Mariarosa; Hasa, Dritan

doi:10.1039/d2ce00162d

Cited by 6 publications

(3 citation statements)

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“…Mechanochemistry (MC) is a method with a long history [ 18 ], which has received renewed interest in recent years, especially in the field of polymer synthesis (MCP) [ 19 ]. Besides reacting solids, modern work in mechanochemical synthesis (MS) includes the use of small amounts of liquid (liquid assisted grinding, LAG [ 20 ]), solid diluents [ 21 ], or even additional polymers [ 22 ] to produce the reaction. Of great interest are those materials which cannot be made by a solution reaction but occur under MCP [ 23 ].…”

Section: Introductionmentioning

confidence: 99%

Mechanochemical Synthesis of Polyanilines and Their Nanocomposites: A Critical Review

Barbero

Acevedo

2022

Polymers

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The mechanochemical synthesis of polyanilines (PANIs), made by oxidative polymerization of anilines, is reviewed. First, previous knowledge of the polymerization reaction in solution is discussed to understand the effect of different parameters: oxidant/monomer ratio, added acid, oxidant, temperature and water content on the properties of the conducting polymers (molecular weight, degradation, doping/oxidation level, conductivity, and nanostructure). The work on mechanochemical polymerization (MCP) of anilines is analyzed in view of previous data in solution, and published data are critically reconsidered to clarify the interpretation of experimental results. A key factor is the production of acids during polymerization, which is often overlooked. The production of gaseous HCl during MCP of aniline hydrochloride is experimentally observed. Since some experiments involves the addition of small amounts of water, the kinetics and heat balance of the reaction with concentrated solutions were simulated. A simple experiment shows fast (<2 min) heating of the reaction mixture to the boiling point of water and temperature increments are observed during MCP in a mortar. The form and sizes of PANI nanostructures made by MCP or solution are compared. The extensive work on the production of nanocomposites by MCP of anilines together with different nanomaterials (porous clays, graphene, carbon nanotubes, metal, and oxide nanoparticles) is also described.

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Section: Introductionmentioning

confidence: 99%

Mechanochemical Synthesis of Polyanilines and Their Nanocomposites: A Critical Review

Barbero

Acevedo

2022

Polymers

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“…The traditional method would include desolvation rather than crystallization; however, such an approach can possibly lead to metastable polymorphs and further problems during process development. Mechanochemical desolvation through polymer-assisted grinding (POLAG) has been recently proposed as an interesting alternative to classical desolvation by heating. , …”

Section: Introductionmentioning

confidence: 99%

“…Mechanochemical desolvation through polymerassisted grinding (POLAG) has been recently proposed as an interesting alternative to classical desolvation by heating. 17,18 Selectivity of a solid for a particular solvent cannot be easily rationalized. Computational techniques have been employed for a mechanistic understanding and to reduce experimental work required for the discovery of new multicomponent solids.…”

Section: ■ Introductionmentioning

confidence: 99%

Competitive Mechanochemical Solvate Formation of Theophylline in the Presence of Miscible Liquid Mixtures

D’Abbrunzo,

Spadaro,

Arhangelskis

et al. 2023

Crystal Growth & Design

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In this study, we investigated the mechanochemical competitive solvate formation of polymorphic Form II of theophylline in the presence of two solvate/hydrate-forming miscible liquids, namely, water and 2-pyrrolidone. It is known that theophylline transforms into a monohydrate in the presence of water, while 2-pyrrolidone gives a monosolvate or a sesquisolvate, depending on the experimental conditions. Different theophyllineto-liquid molar ratios and several water:2-pyrrolidone mixtures were used to understand the competitive formation and/or transformation between these solvates. Interconversion studies between hydrate/monosolvate/sesquisolvate forms were also conducted. The obtained results suggest that water:2-pyrrolidone mixtures have a detrimental effect on the formation of multicomponent phases, as they dramatically reduce the efficiency of incorporation of both liquids in the crystal. In fact, all milling experiments performed in the presence of water:2-pyrrolidone mixtures suggested that a higher stoichiometric ratio is needed to obtain a pure form of a specific solvate. Importantly, additional competitive milling experiments revealed a preferential inclusion of 2-pyrrolidone over water. Based on several experimental datasets performed, we conclude that the propensity of solvate formation in the presence of liquid mixtures is a consequence of a complex interplaying of physicochemical and kinetic factors.

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Achieving Regioselective Control for Mechanochemical Reactions: A Planetary Ball‐Milling, Ru‐Catalyzed Synthesis of 3,4‐ and 3,4,5‐Isoxazoles

Hernandez R.,

Nabavi,

Patterson

et al. 2024

ChemCatChem

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A mechanochemical‐enabled Ru‐catalyzed regioselective synthesis of 3,4‐isoxazoles and 3,4,5‐isoxazoles from terminal and internal alkynes and hydroxyimidoyl chlorides is reported. This solid‐state and solvent‐free approach carefully examines the impact of the milling conditions on regiocontrol in 1,3‐dipolar cycloadditions using mechanochemical means. The study reveals that milling frequency, jar material, and the choice of liquid additive for liquid‐assisted grinding (LAG) significantly influence the catalytic activity of the Ru catalyst. Transmission electron microscope (TEM) analysis confirms the crucial role of coordinating liquid additives such as acetone and cyclopentyl methyl ether (CPME) in stabilizing and reducing the size of the in‐situ formed Ru nanoparticles, which is essential for catalytic activity. The applicability of this protocol is further demonstrated through the synthesis of a library of 3,4‐ and 3,4,5‐isoxazoles from a wide range of terminal and internal alkynes with varying physical states and electronic properties that highlights the potential of this method for the synthesis of more complex target molecules.

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Controlling desolvation through polymer-assisted grinding

Abstract: We demonstrate the ability to controllably desolvate a crystal-solvate system in step-wise fashion through polymer-assisted grinding by varying the type and proportion of polymer agent used. A plausible mechanistic explanation...

Cited by 6 publications

References 53 publications

Mechanochemical Synthesis of Polyanilines and Their Nanocomposites: A Critical Review

Mechanochemical Synthesis of Polyanilines and Their Nanocomposites: A Critical Review

Competitive Mechanochemical Solvate Formation of Theophylline in the Presence of Miscible Liquid Mixtures

Achieving Regioselective Control for Mechanochemical Reactions: A Planetary Ball‐Milling, Ru‐Catalyzed Synthesis of 3,4‐ and 3,4,5‐Isoxazoles

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