Polielektrolitni polihipe hidrogeli za sanacijo onesnaženih voda

doktorska disertacija

Sarah Jurjevec (Avtor), Sebastijan Kovačič (Mentor), David Pahovnik (Komentor)

Povzetek

Brez vode ni življenja. Njeno onesnaževanje danes predstavlja eno najresnejših ekoloških groženj. Sanacija onesnaženih voda je postala nujna. Zato tudi izbrana tema za doktorsko disertacijo Polielektrolitni polihipe hidrogeli za sanacijo onesnaženih voda nikakor ni naključna. %%Pripravili smo visoko porozne polimerne materiale, ki so sposobni iz vode hitro in učinkovito odstraniti različna onesnaževala, kot so npr. ionska organska barvila, težke kovine ali endokrine motilce, z adsorpcijo ali fotokatalitsko razgradnjo. %%V prvem delu disertacije smo z radikalsko polimerizacijo emulzij z visokim deležem notranje faze (HIP emulzije) sintetizirali visoko porozne poliamfolitne monolite ali kroglice (imenovane poliHIPE materiali) na osnovi 2-akrilamido-2-metilpropansulfonske kisline (AMPS), (3-akrilamidopropil) trimetilamonijevega klorida (AMPTMA) in N-vinilformamida (NVF). V primeru amfolitnih poliHIPE monolitov smo raziskali vpliv sestave in mešanja HIP emulzij na porozno morfologijo končnih monolitov, porazdelitev ionskih skupin (%SO3- oz. %NR3+) znotraj monolita ter učinkovitost odstranjevanja organskih barvil iz vode. Naš namen je bil uvesti različno nabite ionske skupine v strukturo poroznih monolitov, da bi iz vodnih raztopin lahko odstranjevali hkrati tako kationska kot anionska organska barvila / nečistoče z mehanizmom absorbcije. Porozni poliamfolitni monoliti so se izkazali kot zelo uspešni pri sočasni adsorpciji kationskega (metilensko modro) in anionskega (eritrozin) barvila iz vode. Pokazali smo, da z enostavnim pristopom mešanja HIP emulzij lahko pripravimo porozne monolitne adsorbente, ki imajo polimerno ogrodje sestavljeno iz različno prepletajočih se polikationskih in polianionskih mrež in imajo izjemne adsorpcijske sposobnosti. V nadaljevanju smo na poliHIPE monolitih iz N-vinilformamida raziskali vpliv vsebnosti zamreževalca in pogojev hidrolitske pretvorbe formamidnih skupin do aminskih skupin. Potrdili smo visoko konverzijo formamidnih skupin do primarnih aminskih skupin, saj sintetiziran poliHIPE material vsebuje ~10 mmol aminskih skupin na gram. Poliaminski poliHIPE ima odlične absorpcijske in adsorpcijske lastnosti, saj je sposoben absorbirati ~100 g vode na gram suhe mase. Poliaminski poliHIPE adsorbent smo testirali za odstranjevanje Cu2+ ionov iz vode, pri čemer je material po samo eni uri delovanja adsorbiral kar 43 % začetne (7,9%10-3 M) koncentracije Cu2+ ionov.%%V nadaljevanju smo s sedimentacijsko polimerizacijo pripravili polielektrolitne poliHIPE materiale v obliki kroglic iz multiplih emulzij. Kroglice smo pripravili na osnovi AMPS oz. AMPTMA ionskih monomerov v kombinaciji z akrilamidom (AAm) v različnih molskih razmerjih in raziskali vpliv kemijske sestave multiplih emulzij (vrsta in vsebnost monomerov, zamreževalca in iniciatorja) na obliko in morfologijo kroglic. Zaradi kombinacije polielektrolitnega značaja in porozne strukture, poliHIPE kroglice v vodi hitro nabreknejo do visoke stopnje, saj ravnotežno vsebnost absorbirane vode dosežejo že po 15 sekundah. Z večjo vsebnostjo ionskih skupin v strukturi kroglic je naraščala tudi ravnotežna vsebnost vode. Maksimalna količina absorbirane vode poliHIPE kroglic na osnovi PAMPS je med 21 in 38 g%g-1, medtem ko je ta vrednost za kroglice na osnovi PAMPTMA med 25 in 43 g%g-1, odvisno od kemijske sestave kroglic. PAMPTAM poliHIPE kroglice smo nadalje testirali kot sušilno sredstvo za sušenje organskih topil in testiranja izvedli s toluenom, diklorometanom, N,N-dimetilformamidom in tetrahidrofuranom. Polielektrolitne poliHIPE kroglice so bile v organskih topilih, v odvisnosti od vrste topila, sposobne v manj kot uri odstraniti med 60 in 95 % začetne vode. %%V nadaljevanju smo z inovativno Sonogashira-Hagihara reakcijo navzkrižnega pripajanja v HIP emulzijah sintetizirali %-konjugirane poliHIPE materiale na osnovi poli(arilenetinilenov) (PAE) iz različnih substituiranih neionskih monomerov, kot so 1,4-dijodobenzen, 1,4-dijodo-2,5-dimetoksibenzen, 2,6-dij

Ključne besede

porozni polimeri;emulzije z visokim deležem notranje faze;polielektroliti;Sonogashira-Hagihara reakcija navzkrižnega pripajanja;konjugirani materiali;čiščenje vode;doktorske disertacije;

Podatki

Jezik:	Slovenski jezik
Leto izida:	2021
Tipologija:	2.08 - Doktorska disertacija
Organizacija:	UM FKKT - Fakulteta za kemijo in kemijsko tehnologijo
Založnik:	[S. Jurjevec]
UDK:	665.652.2:628.19(043.3)
COBISS:	78596867
Št. ogledov:	429
Št. prenosov:	58
Ocena:	0 (0 glasov)
Metapodatki:

Ostali podatki

Sekundarni jezik:	Angleški jezik
Sekundarni naslov:	Polyelectrolyte polyHIPE hydrogels for wastewater remediation application
Sekundarni povzetek:	Water is essential for life. Water pollution is one of the most serious ecological threats we face today. In this dissertation thesis, highly porous polymers are investigated for efficient removal of various pollutants from water (such as ionic organic dyes, heavy metals or endocrine disruptors) by adsorption or photocatalytic degradation. %%In this dissertation, highly porous monoliths or beads (mainly polyHIPE materials) based on 2-acrylamido-2-methylpropanesulfonic acid (AMPS), (3-acrylamidopropyl) trimethylammonium chloride (AMPTMA) and N-vinylformamide (NVF) are studied. The influence of the composition and mixing of the HIPEs on the porous morphology of the final amphoteric polyHIPE monoliths, their distribution of polyion groups (-SO3 or -NR3%) within the monolith and their efficiency in removing organic dyes from water were investigated. The aim of this research was to have both positive and negative ionic groups within the porous morphology in the same monolith, so that both cationic and anionic organic dyes are adsorbed from the aqueous solution simultaneously. Porous polyamphoteric monoliths showed excellent results in the simultaneous adsorption of both cationic (methylene blue) and anionic (erythrosine) dyes from water. Porous monolithic adsorbents were prepared using a simple approach to mixing HIPE and have a polymer backbone of different polycationic and polyanionic networks and showed exceptional adsorption abilities. For the polyHIPE monoliths prepared with N-vinyl formamide, we investigated the influence of the crosslinker and hydrolysis conditions on the conversion of the formamide groups to polyamine. A high conversion to the primary amine was confirmed with almost 10 mmol of groups per gram of polyHIPE material. The synthesized polyamine-polyHIPE exhibits excellent adsorption and absorption properties, about 100 g of water per gram of its dry mass. The polyamine-polyHIPE adsorbent was tested for the removal of Cu2+ ions from water. After 1 hour, the material adsorbed 43% of the initial concentration of Cu2+ ions. %%Polyelectrolyte polyHIPE materials in the form of beads were prepared from multiple emulsions via sedimentation polymerization. The beads were prepared based on AMPS or AMPTMA ionic monomers in combination with acrylamide (AAm) in different molar ratios. We investigated the influence of the compositions of the multiple emulsions (type and proportion of monomers, crosslinker and initiator) on the shape and morphology of the beads. The combination of polyelectrolyte character and porous structure of polyHIPE beads resulted in a high degree of swelling in water, as they reached the equilibrium value of water absorption after only 15 seconds. As the content of ionic monomers increased, the equilibrium value increased and so did the water uptake. The maximum amount of adsorbed water for PAMPS-based polyHIPE beads is about 21-38 (g%g-1), while the PAMPTMA-based beads are 25-43 (g/g). PAMPTMA-based polyHIPE beads were also tested as desiccants for drying organic solvents, such as toluene, dichloromethane, N,N-dimethylformamide and tetrahydrofuran. The polyelectrolyte polyHIPE beads were able to remove between 60 and 95 % of the initial water in organic solvents in less than one hour. %The second part of the PhD studies the synthesis of %-conjugated polyHIPE materials with Sonogashira-Hagihara cross-coupling reaction based on poly(aryleneethynylene) (PAE) from various substituted nonionic monomers (1,4-diiodobenzene, 1,4-diiodo-2,5-dimetoxybenzene, 2,6-diiodo-4-nitrophenol and 2,5-diiodohydroquinone) and ionic monomer (1,4-diiodo-2,5-bis(3-sulfonatopropoxy)benzene). PAE-based polyHIPEs have semiconducting properties at the expense of the %-conjugated backbone, which enables them to photocatalytically degrade dissolved pollutants in water. PAE-polyHIPE have been investigated as photocatalysts for the degradation of various bisphenols under visible light. PAE-polyHIPEs based on 1,4-diiodobenzene achieved
Sekundarne ključne besede:	porous polymers;high internal phase emulsions;polyelectrolytes;Sonogashira-Hagihara cross coupling reaction;conjugated materials;water pollution;Čiščenje vode;Univerzitetna in visokošolska dela;
Vrsta dela (COBISS):	Doktorsko delo/naloga
Komentar na gradivo:	Univ. v Mariboru, Fak. za kemijo in kemijsko tehnologijo
Strani:	XIII, 114 str.
ID:	12906079