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J Am Chem Soc ; 143(27): 10108-10119, 2021 07 14.
Artigo em Inglês | MEDLINE | ID: mdl-34132532

RESUMO

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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