20.500.12556/DKUM-45640 RAZVOJ DENDRIMERNIH poliHIPE NOSILCEV KOT BAZNIH KATALIZATORJEV DEVELOPMENT OF THE polyHIPE CARRIERS AS BASE CATALYSTS PoliHIPE materiali so porozni emulzijsko pripravljeni polimeri, sintetizirani znotraj emulzij z visokim deležem notranje faze (HIPE). Zelo porozna notranja struktura jim daje posebne karakteristike, zato so uporabni pri različnih tehničnih in industrijskih aplikacijah. Raznovrstnost uporabe dosežejo s funkcionalizacijo ter modifikacijo raznih strukturnih parametrov med in po sintezi. Namen diplomskega dela je bila študija zdužitve aminskega dendrimera kot organskega baznega katalizatorja s PoliHIPE polimerom. Z vezavo teh katalizatorjev na polimerne nosilce smo hoteli združiti najboljše lastnosti obeh materialov. Tako bi imeli poleg katalitičnih lastnosti še možnost boljšega izolacijskega postopka produktov iz reakcij, možnost recikliranja takega katalizatorja, znižanja stroškov reakcij, procesi bi lahko potekali hitreje, najpomembnejša pridobitev tega postopka pa bi bila, da bi s tako funkcionaliziranimi polimernimi katalizatorji zmanjšali količino odpadne snovi pri reakcijah, kar bi moralo biti vodilo pri načrtovanju modernih sinteznih postopkov. Uporabili smo aminske dendrimere na osnovi tris-(2-aminoetil)amina. Sintezo dendrimera smo opravili tako, da smo najprej vezali akrilonitril na tris-(2-aminoetil)amin v vodi kot topilu, nakar smo vmesni nitrilni produkt reducirali do amina z LiAlH4 in tako smo dobili prvo generacijo aminskih dendrimerov. Le-te je mogoče uporabiti v namene organokatalize kot bazne katalizatorje v širokem spektru reakcij. Uporabnost tris-(2-aminoetil)amina in iz njega izhajajočih dendrimerov smo preizkušali pri aldolnih reakcijah (Knoevenagelova kondenzacija) kot testnih reakcijah. Tako smo preverili, pod kakšnimi pogoji osnovni aminski katalizator tris-(2-aminoetil)amin katalizira reakcije med benzaldehidom in tremi modelnimi ketoni različnih reaktivnosti (acetofenon, dibenzoilmetan, dimedon) in ugotovili, da se le najbolj reaktiven substrat – dimedon - pretvori v odgovarjajoč produkt kondenzacije. PolyHIPE materials are porous emulsion prepared polymers synthesized within high internal phase emulsion (HIPE). Very porous inner structure provides specific properties which makes them useful in various technical and industrial applications. Diversified applicability is achieved by functionalization and modification of various structural parameters during and after synthesis. The aim of this work was to study synthetic methods of merging of amino dendrimer as organic base catalyst with PolyHIPE polymer. With binding of the catalyst on polymeric carriers, we wanted to combine the best properties of both materials. In this way we would gain - in addition of catalytic properties - the possibility of easier isolation procedure, ability to recycle such a catalyst, reduction of the reactions costs, processes could run faster, but most importantly, such a functionalized polymer catalysts would reduce the amount of waste, and contribute greatly to the preservation of our environment, which is also a guiding principle in the design of modern synthesis processes. We studied amino dendrimers based on tris-(2-aminoethyl)amine compound. The synthesis of dendrimere was carried out first by binding the acrylonitrile on tris-(2-aminoethyl)amine in water as solvent, then the intermediate nitrile product was reduced to amine with LiAlH4, and thus the first generation of amino dendrimers was obtained. This can be used in organocatalysis as base catalysts within a wide range of reactions. We tested the use of tris-(2-aminoethyl)amine and the resulting dendrimers in the aldol reactions (Knoevenagel condensation) as test reactions. In this way we verified under wich circumstances the amine catalyst tris-(2-aminoethyl)amine catalyzes reactions between benzaldehyde and three model ketones with different reactivities (acetophenone, dibenzoylmethane, dimedone) and discovered that only the most reactive substrate – dimedone - changes to corresponding condensation product. reakcije na trdnih nosilcih PoliHIPE polimeri aminski dendrimeri bazni katalizatorji obnovljivi reagenti aldolna kondenzacija solid supported reactions PolyHIPE polymers amine dendrimers base catalysts recycable reagents aldol condensation true true false [G. Kodrič] Slovenski jezik Angleški jezik Diplomsko delo/naloga 2014-08-31 12:37:41 2014-09-11 17:30:46 2022-05-16 03:05:54 2021-05-02 03:19:16 2014 0 Maribor 0 0000-00-00 NiDoloceno NiDoloceno NiDoloceno 0000-00-00 0000-00-00 0000-00-00 544.478-03(043.2) 18134038 URN:SI:UM:DK:GUBSO3DZ UNI_Kodric_Gregor_2014.pdf UNI_Kodric_Gregor_2014.pdf 1 008453FF117604388E64246E9F3F9AB1 d09f21b3f26625ee6571d4850790722b2c3608cfbd610771abd073b2f1ed67f7 30ea72a3-7c0b-11eb-bb7a-00155d0001ca https://dk.um.si/Dokument.php?lang=slv&id=66885 Fakulteta za kemijo in kemijsko tehnologijo 0 0 0