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Priprava emulzij z visokim deležem notranje faze s C-C reakcijami navzkrižnega pripajanja omogoča sintezo visoko poroznih polimernih pen. Tako pripravljene π-konjugirane poliHIPE pene so še posebej zanimive zaradi združevanja 3D makroporozne morfologije tipične za poliHIPE pene in π-konjugiranega ogrodja značilnega za konjugirane mikroporozne polimere. V sklopu magistrskega dela smo uspešno sintetizirali poli(p-fenilen etinilene) s polimerizacijo HIP emulzij in polimerizacijo v raztopini s Sonogashira reakcijo navzkrižnega pripajanja. Pripravljene poliHIPE pene imajo značilno poliHIPE strukturo, medtem, ko imajo polimeri pripravljeni v raztopini 2D cevasto morfologijo. V nadaljevanju smo na substituiranih poliHIPE penah izvedli reakciji demetiliranja in sultoniranja, da bi povečali hidrofilnost π-konjugiranega ogrodja. Uspešnost funkcionalizacije smo spremljali s FTIR in NMR spektroskopijo ter elementno analizo. Rezultati kažejo, da je bila reakcija sultoniranja uspešna v primeru poli(p-dimetoksibenzena) in neuspešna pri poli(p-nitrofenolu). V zadnjem delu magistrske naloge smo želeli izvesti sintezo substituiranih poli(p-fenilen vinilenov) z emulzijskim templatiranjem s Heckovo reakcijo navzkrižnega pripajanja. Heckovo navzkrižno pripajanje v emulziji nam ni uspelo, zato smo pripravili poli(p-fenilen vinilene) s polimerizacijo v raztopini. Rezultati kažejo, da so za Heck reakcijo primernejša polarna topila in visoke temperature. Z morfološko karakterizacijo smo potrdili klasično cvetačasto morfologijo. Določili in primerjali smo tudi specifično površino (BET) poli(p-fenilen etinilenov) in poli(p-fenilen vinilenov) pripravljenih s polimerizacijo v raztopini in ugotovili, da 2D cevasta morfologija sintetizirana s Sonogashira reakcijo daje višje površine kot cvetačasta morfologija sintetizirana s Heckovo reakcijo. High internal phase emulsions and C-C coupling reactions is a powerful combination for the synthesis of highly porous polymer foams, so-called polyHIPE foams. As-synthesised π-conjugated microcellural polyHIPE foams prepared by this combination are an interesting class of materials as they combine the 3D-interconnected macroporous morphology typical of polyHIPE foams and π-conjugated macromolecular structure typical of conjugated microporous polymeric materials. Here in this work, poly(p-phenylene ethynylene) and poly(p-phenylene vinylenes) have been successfully synthesised via HIPE and solution polymerization using Sonogashira-Hagihara and Heck-Mizoroki coupling reactions, respectively. HIPE polymerization using Heck-Mizoroki coupling reaction failed, while Sonogashira-Hagihara coupling reaction in HIPE was successfull. Both types of coupling reactions proceeds well in solutuions. As-synthesised polyHIPE foams possess typical 3D-interconnected macroporous morphology, whereas solution polymerization yielded 2D tube-like morphology in case of Sonogashira-Hagihara coupling reaction and cauliflower morphology in case of Heck-Mizoroki coupling reaction. Both morphologies of poly(p-phenylene ethynylenes) and poly(p-phenylene vinylenes) obtained by solution polymerization have been further investigated by nitrogen sorption analysis and specific surface area was determined using B.E.T. model. In order to increase the hydrophilicity of polyHIPE foams, further functionalization was performed on substituted poly(p-phenylene ethynylene)s via sulfonation. Success of functionalization was followed by FTIR, NMR and elemental analysis. Results indicated successful sulfonation of poly(p-dimetoxybenzene), while sulfonation of poly(p-nitrophenol) failed. |
