Sinteza in funkcionalizacija makroporoznih poliakrilatov

doktorska disertacija

Janja Majer (Avtor), Peter Krajnc (Mentor)

Povzetek

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 radikalna polimerizacija;poliHIPE;sinteza na trdni fazi;organske reakcije;hiperzamreženje;glicil metakrilat;funkcionalizacija polimerov;doktorske disertacije;

Podatki

Jezik:	Slovenski jezik
Leto izida:	2016
Tipologija:	2.08 - Doktorska disertacija
Organizacija:	UM FKKT - Fakulteta za kemijo in kemijsko tehnologijo
Založnik:	[J. Majer]
UDK:	66.095.26:678.744.33.01(043.3)
COBISS:	19912982
Št. ogledov:	2199
Št. prenosov:	240
Ocena:	0 (0 glasov)
Metapodatki:

Ostali podatki

Sekundarni jezik:	Angleški jezik
Sekundarni naslov:	Synthesis and functionalization of macro-porous polyacrylate
Sekundarni povzetek:	Highly porous polymers from different acrylic derivatives were prepared by free radical polymerization of a water-in-oil and oil-in-water high internal phase emulsions. Acrylic acid, acrylamide and methylenebisacrylamide were used as an acrylic and 2-hydroxyethyl methacrylate, glycidylmethacrylate and ethyleneglycol dimethacrylate were used as acrylate derivatives. Copolymers were further functionalised and their reactivities were compared through a variety of organic reactions. PolyHIPEs based on acrylic acid-co-acrylamide crosslinked with methylenebisacrylamide were prepared at different molar ratios of monomers, in order to examine the influence of the anhydride formation on the conversion of carboxylic groups to the acid chloride using thionyl chloride. 2-hydroxyethyl methacrylate based polyHIPEs were also successfully functionalised with different reagents, without involving the neighbouring ester group to undergo hydrolysis. After successful functionalization with thionyl chloride, further functionalizations with amine reagents were carried out to demonstrate the reactive capabilities and potentials of as-obtained polyHIPEs to be used as carriers for Solid Phase Organic Synthesis (SPOS). The second part of the dissertation describes the preparation and functionalization of glycidyl methacrylate (GMA) based polyHIPEs crosslinked with ethylene glycol dimethacrylate (EGDMA). The purpose of functionalizing GMA polyHIPE materials was to prepare carriers for protein separation with high binding capacities on one hand and to explore the possibility to increase specific surface area through the hyper-crosslinking of the epoxy groups on the other hand. The aim of hyper-crosslinking was the formation of micro- and/or mesoporosity via formed links, which would subsequently increase the volume of micro- and/or mesopores and thus the specific surface area of the material. In that respect, the functionalization was performed with two different types of amine reagents, linear and branched, and the influence of solvents and temperature on the reaction conditions was studied. The conversion yields were between 20 % and 45 %. Afterwards, the relative ion capacity K (/) and dynamic binding capacity (DBC) was determined in comparison with GMA polyHIPE and commercially available macroporous GMA CIM disk (Convective Interaction Media, Bia Separations). For GMA polyHIPE material K (/) and DBC was measured to be 89.7 and 59.6 mg / mL respectively, while for macroporous GMA CIM disk K (/) and DBC were 203 and 38.8 mg / mL, respectively. It can be concluded that the relative ionic capacity of GMA polyHIPE material is 55 % lower but dynamic bonding capacity is 65 % higher. In order to increase the specific surface area of GMA polyHIPE materials, hypercrosslinking of the epoxy groups was performed. Comparatively, two different approaches were used, a post-polymerisation and in-situ hyper-crosslinking. In the case of post-polymerisation hyper-crosslinking approach the GMA polyHIPEs were suspended in a suitable solvent wherein different amine reagents were added. Regardless to the conditions applied (e.g. temperature, time, solvents, amine reagents) no substantial increases of the specific surface areas has been found. Opposite to post-polymerisation hypercrosslinking we found an increase of the specific surface areas in the case of the in-situ approach. Herein, amine reagents were mixed together with monomers into the continuous phase of HIP emulsions and hyper-crosslinking was carried out simultaneously with the polymerisation. In that case, we observed an increase of the specific surface area between 100 and 400 %. Accordingly, also the volume of the smallest mesopores (1.9 - 2.1 nm) has increased, as was determined using the Barrett-Joyner-Halenda (B.J.H.) method thus confirming the hypothesis of the mesopores formation between the newly formed links.
Sekundarne ključne besede:	high internal phase emulsion;HIPEs;free radical polymerisation;energy epolyHIPE;solid phase organic synthesis;organic reactions;hyper-crosslinking;glycidyl methacrylate;polymer functionalization;Poliakrilati;Disertacije;
URN:	URN:SI:UM:
Vrsta dela (COBISS):	Doktorska disertacija
Komentar na gradivo:	Univ. v Mariboru, Fak. za kemijo in kemijsko tehnologijo
Strani:	XV, 98 f.
ID:	9170902