Iskanje po katalogu digitalne knjižnice

Opis: PolyHIPEs are highly porous polymers with an interconnecting porous structure. They have found usage in the removal of pollutants, water clean-up, oil spill removal, catalysis, controlled release of active compounds, wound dressing and tissue engineering. The wide applicability of polyHIPEs is possible through their inherent porosity and chemical diversity. The aim of this dissertation was to increase the chemical diversity of polyHIPEs, develop an efficient method for the synthesis of polyHIPE beads and to use natural resources for the synthesis of polyHIPEs, subsequently, paving the pathway to more sustainable synthetic procedures. PolyHIPEs tend to have poor mechanical properties, therefore, it was crucial to investigate the influence of the internal phase volume, initation type (photo vs thermal) and monomer functionality on the mechanical and morphological properties of thiol-ene polyHIPEs. The results show that the main factors influencing the morphological and mechanical properties are the monomer structure and the internal phase volume. Besides the inherent porosity and chemical versatility typical of polyHIPEs, they can also be produced in various shapes, e.g., monoliths, membranes and beads. Therefore, the dissertation also focuses on the synthesis of polyHIPE beads. The polyHIPE beads were produced through the usage of water-in-oil-in-water (W/O/W) multiple emulsions. To enable the synthesise of open porous polyHIPE beads, thiol-ene polymerisation was combined with photopolymerisation to guarantee a rapid polymerisation prior the break-down of the multiple emulsion. Consequently, it was possible to synthesise polyHIPE beads. The first study showed that by altering the thiol to acrylate ratio in favour of the acrylate the degradation rate of the synthesised polyHIPE beads gets reduced. Additionally, it was demonstrated that the beads can be readily functionalised with allyl amine and used for the adsorption of methylene blue (12.0 mg/g in 24 hours). The next study combined polyHIPE beads with magnetic nanoparticles (MNPs) to produce magnetic polyHIPE beads which were used for the removal of Pb2+. To produce the magnetic polyHIPE beads, magnetic nanoparticles (MNPs) were added to the organic phase. The MNPs get incorporated into the polymer-network after the polymerisation, therefore, forming magnetic polyHIPE beads. The MNPs were shown to influence the morphology and the size of the beads. Additionally, the polyHIPE beads were shown to remove up to 97.0 % of Pb2+ after 24 hours from a 2.9 mg/L solution of Pb2+. In the last study related to the synthesis of polyHIPE beads, functional polyHIPE beads were produced and then functionalised to enable the binding of the enzyme invertase. These beads were then utilised for the hydrolysis of sucrose. The conversion of sucrose to glucose and fructose was 100% after 60 minutes for the polyHIPE beads, while the conversion for non-porous beads was only 6.5%. The last part of the thesis focused on more sustainable/natural approaches to polyHIPE synthesis. The first study utilised limonene as a replacement to conventional solvents (e.g., cyclohexane) in the production of O/W HIPEs and the polymerisation thereof into polyHIPEs. It was shown that limonene can be used as an efficient replacement in the production of polyHIPEs. The next study used natural resources (terpenoids) which were modified to contain polymerisable units, which were used for the synthesis of terpenoid-based polyHIPEs. The synthesised monomers were then crosslinked with 5 and 10 mol. % TMPTA to form polyHIPEs, consequently producing porous polymers. The last study in this thesis used the terpenes limonene, carvone and myrcene to produce bio-based polyHIPEs by utilising multifunctional acrylates (PETA and TMPTA) as the comonomers. This study demonstrates that it is possible to prepare polyHIPEs from commercially available terpenes, therefore, moving the field of polyHIPEs into a more sustainable direction.
Ključne besede: HIPE, PolyHIPE, Multiple Emulsions, Functional polyHIPEs, Natural Polymers, Terpenes
Objavljeno v DKUM: 08.12.2023; Ogledov: 456; Prenosov: 76
Celotno besedilo (8,08 MB)

Opis: Naravni polimeri v vse večji meri nadomeščajo sintetične ekvivalente iz fosilnih goriv. Za njihovo sintezo se med drugim uporabljajo terpeni, ki so široko dostopni kot stranski produkti pri predelavi citrusov. Polimeri sintetizirani iz le-teh imajo nizko toksičnost in so potencialno biorazgradljivi, zato se intenzivno raziskujejo kot prekurzorji za razvoj trajnostnih polimerov. V diplomskem delu smo z uporabo emulzij z visokim deležem notranje faze, t.i. HIPE, sintetizirali porozne poliHIPE materiale na osnovi izbranih terpenov, tj. limonena in mircena. Pripravili smo kopolimere različnih razmerij terpena proti akrilatu (1:1, 1:3 in 3:1), pri čemer smo kot drugi monomer v organski fazi uporabili trimetilolpropan triakrilat (TMPTA) ob dodatku surfaktanta Hypermer B246, iniciatorja AIBN in toluena. Poleg tega smo glede na celotni volumen emulzije dodali 80 vol.% vodne faze. Na podlagi različnih razmerij smo ugotavljali vključenost terpena v polimeru in opazovali vpliv na morfologijo ter poroznost. Vzorce smo očistili v Soxhletovem aparatu in karakterizirali z različnimi metodami. Kemijsko sestavo smo preverili z elementno analizo, iz dobljenih vrednosti smo izračunali vključenost terpena v našem vzorcu. Z elektronsko vrstično mikroskopijo (SEM) smo preverili ali imajo vzorci ustrezno, za poliHIPE značilno, porozno strukturo sestavljeno iz primarnih in sekundarnih por, ki smo jih tudi izmerili. Po metodi BET smo izmerili specifične površine, določili smo še celokupno in skeletno gostoto iz katere smo izračunali poroznost. Nenazadnje pa smo posneli FTIR spektre s katerimi smo se prepričali o uspešnosti sinteze.
Ključne besede: poliHIPE, terpeni, naravni polimeri, HIPE, kopolimeri
Objavljeno v DKUM: 31.08.2022; Ogledov: 712; Prenosov: 122
Celotno besedilo (6,72 MB)

Opis: V diplomski nalogi z naslovom Vpliv zamreženja porozne poli(akrilne kisline) na absorptivne lastnosti smo sintetizirali porozno poli(akrilno kislino). Za pridobivanje poroznih materialov obstaja več različnih tehnik, mi smo se posluževali polimerizacije kontinuirne faze emulzije z visokim deležem notranje faze (HIPE polimerizacija). Pri naši sintezi je vlogo monomera igrala akrilna kislina, kot zamreževalo pa smo uporabljali N,N ́-metilenbisakrilamid (MMBA). Za nastanek emulzije so nujno potrebni še iniciator, mi smo uporabljali amonijev persulfat (APS), surfaktant, mi smo uporabljali Triton X-405, ter redukcijsko sredstvo, mi smo uporabljali tetrametiletilendiamin (TEMED). Reakcija je potekala po verižni radikalski polimerizaciji. Emulzija, ki smo jo pripravili je bila tipa olja v vodi. Kot notranjo fazo smo uporabljali topilo toluen. Materiale pred karaterizacijo je bilo potrebno očistiti z ekstrakcijo v Soxhletovem aparatu, kjer smo odstranili notranjo fazo, pri tem pa smo uporabljali topilo metanol. Sintetizirali smo več različnih materialov in sicer pri enem nismo dodali vodne raztopine NaOH, pri ostalih treh pa smo spreminjali stopnjo zamreženosti, ki je varirala med 10 %, 25 % in 50 %. Po sintezi smo del materiala pustili v metanolu, del smo ga pa dali sušiti v vakuumski sušilnik. Nato smo opazovali sestavo in absorptivno zmogljivost za vodni medij. Absorptivno zmogljivost smo preverjali pri materialu, ki se ni sušil v vakuumskem sušilniku, in sicer v deionizirani vodi. Pri materialih, ki so se sušili v vakuumskem sušilniku smo preverjali absorptivno zmogljivost v destilirani vodi, 0.1 M raztopini NaOH in 0.1 M raztopini HCl. Ugotovili smo, da se materili, ki imajo višjo stopnjo zamreženosti slabše absorbirajo kot materiali z nižjo stopnjo zamreženosti. Na samo absorptivnost vpliva tudi prisotnost baze v sami sestavi. Če je prisotna baza, nastane material z nabito hidrofilno skupino COONa, ki ima dobre absorptivne zmogljivosti. Če pa ni prisotna baza, nastane porozni material s kislinsko skupino COOH, ki ima slabše absorptivne zmogljivosti.
Ključne besede: emulzija, zamreženost, absorptivne lastnosti, HIPE, poli(akrilna kislina)
Objavljeno v DKUM: 08.10.2020; Ogledov: 1494; Prenosov: 117
Celotno besedilo (1,63 MB)

Opis: This thesis aims to explain the process of porous bead synthesis. The porous beads were prepared from a multiple emulsion water-in-oil-in-water (W/OW) system. The W/O/W multiple emulsion was made up of a High Internal Phase Emulsion (HIPE (primary emulsion)) and a suspension phase. The HIPE consisted of pentaerythritol tetrakis (3 mercaptopropionate) (TT) in combination with either divinyl adipate (DVA) or trimethylolpropane triacrylate (TMPTA) and an internal phase volume fraction of 80 %. The suspension phase consisted of an aqueous phase with dissolved surfactants which stabilised the secondary emulsion. The surfactants which stabilised the secondary emulsion were polyvinylpyrrolidone K30 (PVP K30) and polyvinylpyrrolidone K90 (PVP K90). The polymerisation was carried out thermally at first for 24 hours and later under UV light and daylight, as the thermally initiated polymerisation was unsuccessful due to coalesence. The beads that were obtained using the photoinitiated polymerisation were porous with a mostly bicontinuous structure and varying diameters. The viscosity of the primary emulsion (HIPE) had the greatest influence on the stability of the entire W/O/W emulsion. By adding more than 5 wt. % of toluene to the primary emulsion, the emulsion broke down and did not successfully polymerise. Another important factor was the ratio of the functional groups in the case of TT-co-TMPTA, which greatly affected the yield and structure of the obtained beads. The diameters of the spherical particles were dependent on the viscosity, monomer ratio and surfactant used in the suspension phase. The inner structure of the beads was mostly bicontinuous with occasional pores that resembled a polyHIPE structure. The obtained beads had a yield of up to 80 % in the case of TT-co-DVA and a yield of up to 90 % in the case of TMPTA-co-DVA
Ključne besede: polyHIPE, thiol-ene, suspension polymerisation, porous beads, HIPE
Objavljeno v DKUM: 17.09.2019; Ogledov: 1592; Prenosov: 233
Celotno besedilo (3,56 MB)

Opis: Z verižno radikalsko polimerizacijo voda/olje in olje/voda emulzij z visokim deležem notranje faze smo pripravili visoko porozne kopolimerne nosilce na osnovi različnih akrilnih derivatov. Kot akrilne derivate smo uporabili akrilno kislino, akrilamid, metilenbsiakrilamid, 2-hidroksietil metakrilat, glicidilmetakrilat in etilenglikoldimetakrilat. Uspešno pripravljene visoko porozne kopolimere smo funkcionalizirali in primerjali njihovo reaktivnost z različnimi organskimi reakcijami. Kopolimerne nosilce na osnovi akrilne kisline in akrilamida, zamrežene z metilenbisakrilamidom, smo pripravili z različnimi molarnimi razmerji monomerov ter proučili vpliv tvorbe anhidrida na stopnjo konverzije pri funkcionalizaciji s tionil kloridom do kislinskega klorida. Prav tako smo uspešno funkcionalizirali 2-hidroksietil metakrilatni poliHIPE material z različnimi reagenti, ne da bi pri tem prišlo do hidrolize sosednje esterske vezi. Po uspešni funkcionalizaciji do kislinskega klorida v primeru kopolimera akrilne kisline in akrilamida oz. alkil halogenida v primeru 2-hidroksietil metakrilatnega poliHIPE materiala smo izvedli nadaljnjo funkcionalizacijo z aminskimi reagenti, ter tako dokazali primernost za nosilce za sinteze na trdni fazi (ang. Solid Phase Organic Synthesis, SPOS) . V drugem delu smo pripravili polimerne nosilce na osnovi glicidilmetakrilata (GMA) zamreženega z etilenglikol dimetakrilatom (EGDMA) in proučili reakcijske pogoje funkcionalizacije epoksi skupin. Namen funkcionalizacije GMA poliHIPE materialov je bil pripraviti nosilce z ionsko izmenjevalnimi skupinami na površini por ter preučitev možnosti naknadnega zamreženja oz. hiperzamreženja preko epoksi skupin. Na račun novo nastalih povezav med polimernimi verigami bi povečali volumen mikro- oz. mezopor in s tem tudi specifično površino materiala. V ta namen smo funkcionalizacijo GMA poliHIPE materialov izvedli z dvema tipoma aminskih reagentov, linearnimi in razvejanimi in najprej raziskali vpliv topila in temperature na reakcijske pogoje funkcionalizacije. Po uspešni funkcionalizaciji je bila stopnja pretvorbe glede na uporabljen aminski reagent med 20 % in 45 %. Določili smo relativno ionsko kapaciteto K(/) in dinamično vezno kapaciteto (DBC) primerjalno za GMA poliHIPE in komercialno dostopen makroporozni GMA CIM disk (ang. Convective Interaction Media, Bia Separations). Za GMA poliHIPE material smo izmerili K(/) 89.7 in DBC 59.6 mg/mL, za makroporoznim poliGMA CIM nosilec pa K(/) 203 in DBC 38.8 mg/mL. Iz rezultatov lahko zaključimo, da je relativna ionska kapaciteta je 55 % manjša v primeru GMA poliHIPE materiala, dinamična vezna kapaciteta pa je 65 % višja. Proučili smo tudi možnosti zvišanja specifične površine GMA poliHIPE materialov z naknadnim zamreženjem oz. hiperzamreženjem preko epoksi skupin. Primerjalno smo uporabili dve različni metodi, post-polimerizacijsko ter in-situ hiperzamreženje. V primeru post-polimerizacijskega hiperzamreženja smo uspešno sintetiziran GMA poliHIPE material suspendirali v primernem topilu in dodali različne aminske reagente. Ne glede na pogoje (temperatura, čas, topila, koncentracija reagenta, stopnja zamreženja GMA poliHIPE materiala) bistvenih zvišanj specifičnih površin nismo zaznali. Nasprotno pa je bilo v primeru in-situ reakcij. Aminske reagente smo umešali skupaj z monomerom GMA in zamreževalom etilenglikol dimetakrilat (EGDMA) že v fazi priprave HIP emulzij ter izvedli hiperzamreženje istočasno s polimerizacijo. V tem primeru smo zabeležili povišanje specifične površine med 100 in 400 %. Skladno s specifično površino se je povišal tudi volumen najmanjših mezopor (1.9 – 2.1 nm), ki smo ga določili s pomočjo Barrett-Joyner-Halend (B.J.H.) metode po dušikovi sorpciji. Hipoteza tvorbe mezopor med novo nastalimi povezavami polimernih verig se je tako potrdila.
Ključne besede: emulzije z visokim deležem notranje faze (HIPE), verižna radikalska polimerizacija, poliHIPE, sinteza na trdni fazi, organske reakcije, hiperzamreženje, poli(akrilna kislina), poli(2-hidroksietilmetakrilat), glicidil metakrilat, funkcionalizacija polimerov.
Objavljeno v DKUM: 25.10.2016; Ogledov: 2923; Prenosov: 285
Celotno besedilo (5,54 MB)