Novel cross-linked polystyrenes with large space network as tailor-made catalyst supports for sustainable media

•Design and synthesis of novel solid catalytic systems specifically developed for sustainable reaction media.•Preparation and characterization of novel polystyrene-based gel-type supports and corresponding polystyrene-immobilized-TBD/TEA.•Ring opening of phenyl glycidyl ether by thiophenol.•Knoevenagel condensation of benzaldehyde with ethyl cyanoacetate.•Michael addition of butanethiol to (E)-benzilydene acetone.

A novel class of polystyrene-based gel-type resins (SPACeR, SP), containing the large 1,4-bis(4-vinylphenoxy)benzene cross-linker, is introduced; SP-immobilized 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) and triethylamine (TEA) bases are synthesized and characterized in terms of their structural, thermal and morphological features, and their catalytic efficiency in a series of fundamental chemical transformations under solvent-free conditions is investigated.

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