Reaction of ethoxycarbonylcarbene with n-hexadecane and n-docosane

Forbes, A. D.; Wood, J. L.

doi:10.1039/j29710000646

Cited by 10 publications

(6 citation statements)

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“…The activation energy E A is determined to be 106 kJ/mol. 30,31 This value is rather low in comparison to a diazo malonate crosslinker (E A = 143 kJ/mol) that was used in previous work. 2 The lower activation energy can be explained by the substitution of an ester group by a phenyl group, which has less of a stabilizing effect on the diazo group.…”

Section: ■ Results and Discussionmentioning

confidence: 85%

Thermally Induced Cross-Linking of Polymers via C,H Insertion Cross-Linking (CHic) under Mild Conditions

et al. 2021

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The focus of studies performed so far on the formation of surface-attached polymer networks by C,H insertion cross-linking (CHic) reaction has been largely on photochemical activation. This study describes the thermal activation of the formation of (surface-attached) polymer networks under comparably mild conditions. A novel cross-linker, based on a diazo phenyl ester group, is incorporated into various copolymers, which are subsequently deposited on solid substrates. Upon activation, the cross-linker moieties generate carbene intermediates, which lead to rapid, complete cross-linking of the whole film and simultaneous surface attachment to various organic materials via CHic. Although this system requires only comparably mild conditions (i.e., below 100 °C) to become activated, a long shelf life at room temperature is observed. The presented system might be useful in a wide range of applications, from coatings to rather complex geometries. We demonstrate the covalent binding of protein-repellent thin films to the inner surface of (rubber) tubes and the generation of patterned structures by a “branding iron” approach. For this a hot structure is pressed onto a diazo polymer coated surface, leading in the contact zone to fast cross-linking while in all other areas the polymer remains soluble and is washed off during subsequent extraction.

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Section: ■ Results and Discussionmentioning

confidence: 85%

Thermally Induced Cross-Linking of Polymers via C,H Insertion Cross-Linking (CHic) under Mild Conditions

et al. 2021

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“…When the logarithm of the initial‐rate constant k , is plotted versus the inverse temperature, the activation energy E A is determined. These activation energies are approximately 20 kJ mol −1 higher than those of typical low‐molecular‐weight diazo compounds, for example, ethyl diazoacetate (125 kJ mol −1 ) . This finding seems to be reasonable because diazomalonates contain two stabilizing ester groups.…”

Section: Methodsmentioning

confidence: 75%

Malonic Acid Diazoesters for C−H Insertion Crosslinking (CHic) Reactions: A Versatile Method for the Generation of Tailor‐Made Surfaces

Kotrade¹,

Rühe²

2017

Angewandte Chemie

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A simple and versatile method for the modification of a broad spectrum of surfaces with thin polymer films through the thermally or photochemically induced generation of surface‐attached polymer networks is reported. The system is based on copolymers containing diazomalonate groups, which can be activated by heat or light. To this end, the copolymers are deposited from solution onto solid substrates by standard techniques of thin‐film deposition (spin coating, dip coating). Upon activation the diazomalonate group decomposes and forms a carbene, which induces C−H insertion crosslinking (CHic) reactions. In the course of this process network formation and covalent surface attachment occur at the same time. The crosslinking process proceeds very rapidly, especially when the carbenes generated in the activation process cannot undergo Wolff‐rearrangement. The presented system can be used for the generation of a wide range of polymer layers and microstructures on a broad spectrum of surfaces.

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“…44 A polymer of ethoxycarbonylcarbene could form presumably by repeated reaction of the carbene with itself or with ethyl diazoacetate, and the bulk of the carbine–carbene or carbene–diazoacetate reactions occurs in the α-position. 45 In this work, we determined the concentration of DEF and DEM separately and took the sum as the concentration of dimmers. The yield of dimmers is denoted as the ratio of dimmers concentration to 0.5 C EDA,0 .…”

Section: Resultsmentioning

confidence: 99%

Thermal Decomposition of Ethyl Diazoacetate in Microtube Reactor: A Kinetics Study

Xin

2018

ACS Omega

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Ethyl diazoacetate (EDA) commonly experiences intensive decomposition as well as complex conversion concerning safety and efficiency. In this work, a careful kinetics study on the thermal decomposition of EDA was isothermally conducted in a microtube reactor to establish a mechanism-based kinetic model. The model parameters were well calibrated with experimental data including the yield of dimmers and the conversion of EDA, confirming the rationality of the proposed three-step reaction route. It allows the model to concisely describe the complex species transformations during EDA decomposition, which is unavailable for an apparent kinetic model. Considering an isothermal reaction system and the tolerance of EDA consumption by thermal decomposition, this work could help reveal the requirement on the kinetic characteristics of the desired catalytic reaction in which EDA is involved, as a reference on reaction process modeling and regulation.

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Reaction of ethoxycarbonylcarbene with n-hexadecane and n-docosane

Cited by 10 publications

References 0 publications

Thermally Induced Cross-Linking of Polymers via C,H Insertion Cross-Linking (CHic) under Mild Conditions

Thermally Induced Cross-Linking of Polymers via C,H Insertion Cross-Linking (CHic) under Mild Conditions

Malonic Acid Diazoesters for C−H Insertion Crosslinking (CHic) Reactions: A Versatile Method for the Generation of Tailor‐Made Surfaces

Thermal Decomposition of Ethyl Diazoacetate in Microtube Reactor: A Kinetics Study

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