Functionalization of thiol groups in porous polythiolens

Namen te diplomske naloge je bil sintetizirati visoko porozne polimerne materiale s tiol-en klik fotopolimerizacijo, pri kateri smo kot vir tiolnih skupin uporabili pentaeritritol tetrakis (3-merkaptopropionat), kot vir vinilnih skupin pa akrilata trimetilolpropan triakrilat in 1,6-heksandiol diakrilat ter ester diviniladipat. Sintezni postopek je temeljil na fotopolimerizaciji kontinuirne faze emulzije z visokim deležem notranje faze tipa voda v olju, katere rezultat je visoko porozna morfologija materiala. Kot vir vinilnih skupin smo uporabili akrilate in ester zato, ker se med seboj razlikujejo v reaktivnosti. Ker so estri bolj reaktivni kot akrilati smo pričakovali, da v tovrstnih materialih na račun pogostejše abstrakcije vodikovega atoma iz druge molekule tiola od strani estra v propagaciji, v materialu ne bo ostalo skupin, ki jih lahko v nadaljevanju izkoristimo za različne aplikacije. Ostanejo pa v primeru akrilatov, ki pa imajo večjo težnjo po homopolimerizaciji. Mi smo sintetizirane polimere uporabili kot nosilce za bakrovo in kobaltovo sol in za oksidativno reakcijo s katero smo tiolne skupine pretvarjali v disulfidne skupine. Sintetizirani in funkcionalizirani material smo ustrezno okarakterizirali s FTIR in Ramansko spektroskopijo, elementno analizo, vrstičnim elektronskim mikroskopom, porozimetrom in Ellmanovim testom. Sinteza polimernih materialov je bila uspešna. Kot rezultat fotopolimerizacije smo dobili elastične monolitne materiale s tipično poliHIPE morfologijo v primeru uporabljenih akrilatov in bikontinuirno morfologijo v primeru estra. Polimera z akriltanim monomerom sta vsebovala večji delež prostih tiolnih skupin kakor material z estrskim monomerom. Reakcija z jodom v acetonitrilu, ki pretvarja tiolne skupine v disulfidne, je bila z Ramansko spektroskopijo uspešno potrjena le za akrilatna monomera.The aim of this work was to synthesise highly porous polymeric materials by thiol-one click photopolymerization using pentaerythritol tetrakis (3-mercaptopropionate) as the source for the thiol groups and acrylate trimethylolpropane triacrylate and 1,6-hexanediol diacrylate and divinyl diphosphate ester as the source for the vinyl groups. The synthesis procedure was based on the photopolymerization of a continuous phase emulsion with a high proportion of a water-in-oil type internal phase, resulting in a highly porous material morphology. Acrylates and esters were used as sources of vinyl groups because they differ in reactivity. Since esters are more reactive than acrylates, we expected that in this type of material, due to the more frequent abstraction of the hydrogen atom from the second thiol molecule on the ester side of the propagation, no groups would remain in the material that could be further used for various applications. In the case of acrylates, which have a greater tendency to homopolymerize, they are retained. We used the synthesised polymers as supports for the copper and cobalt salts and for the oxidative reaction that converted the thiol groups into disulfide groups. The synthesised and functionalized material was characterised by FTIR and Raman spectroscopy, elemental analysis, in-line electron microscopy, porosimeter and Ellman test. The synthesis of the polymeric materials was successful. Photopolymerization resulted in elastic monolithic materials with typical polyHIPE morphology in the case of the acrylates used and bicontinuous morpholgy in the case of the ester. The two polymers with the acrylate monomer contained a higher proportion of free thiol groups than the material with the ester monomer. The reaction with iodine in acetonitrile, which converts the thiol groups to disulfide groups, was successfully confirmed by Raman spectroscopy only fort he acrylates monomers