Title Sinteza kovalentno umreženog vodljivog polimera PEDOT-g-PEG Title (english) Synthesis of covalently crosslinked conductive polymer PEDOT-g-PEG Author Antonijo Ćosić Mentor Zvonimir Katančić (mentor)Committee member Zvonimir Katančić (predsjednik povjerenstva)Committee member Domagoj Vrsaljko (član povjerenstva)Committee member Zlata Hrnjak-Murgić (član povjerenstva)Granter University of Zagreb Defense date and country 2023-07-14, Croatia Scientific / art field, TECHNICAL SCIENCES Abstract Od svog otkrića elektrovodljivi polimeri privukli su pozornost zbog svojstva otpornosti na koroziju, električne vodljivosti i niske gustoće. Svojstvo električne vodljivosti omogućuje naizmjenični raspored jednostruke i dvostruke veze te uvođenje slobodnog nositelja naboja. Jedan od glavnih predstavnika elektrovodljivih polimera je poli(3,4-etilendioksitiofen) (PEDOT) zbog svoje dobre kemijske stabilnosti, biokompatibilnosti, niskih troškova proizvodnje te električne vodljivosti u rangu poluvodiča. Uvođenjem bočnih grana
poli(etilen-glikola) (PEG) poboljšavaju se istezljivost i savitljivost zbog uspostave nekovalentnog umreženja vodikovim vezama što omogućuje potencijalnu primjenu u polju nosive elektronike. Dodatkom sredstva za umrežavanja moguće je ostvariti potpuno kovalentno umreženje što dodatnu povećava istezljivost, a povećava se i otpornost na kemikalije. Sinteza graft kopolimera provodila se u četiri koraka. U prvom koraku sintetizirao se bromom funkcionalizirani monomer tiofena, ThBr, a u drugom makroinicijator PEDOT-Br. Potom je sintetiziran graft kopolimer PEDOT-g-PEG graftiranjem bočnih lanaca PEG-a na glavni lanac PEDOT-Br radikalskom polimerizacijom prijenosom atoma (ATRP). U četvrtom koraku proveden je ponovno ATRP uz dodatak sredstva za umrežavanje
(2-okso-1,3-dioksolan-4-il)metil metakrilat (GCMA) kako bi se dobio kovalentno umreženi vodljivi polimer X-PEDOT-g-PEG. Dobiveni uzorci karakterizirani su nuklearnom magnetskom rezonancijom (NMR), infracrvenom spektroskopijom s Fourierovom transformacijom (FTIR), termogravimetrijskom analizom (TGA)i diferencijalnom pretražnom kalorimetrijom (DSC).
Na temelju dobivenih uzoraka pripremljene se tinte za inkjet ispis na savitljivu podlogu poliuretana (PU). Ispisanim slojevima na podlozi ispitana je električna provodnost te mehaničko svojstvo istezljivosti. Rezultati dobiveni FTIR i NMR analizom potvrđuju uspješnost sinteze PEDOT-g-PEG, dok DSC analiza pokazuje temperaturu staklastog prijelaza ispod tjelesne temperature (37 °C) što omogućuje savitljivost graft kopolimera u kontaktu s kožom. Vrijednosti električne provodnosti su u rangu poluvodiča, a istezanjem od 50 % ne zaostaje trajna deformacija te nije uočena značajna promjena elektrokemijske aktivnosti. Na temelju cjelokupnih rezultata sintetizirani graft kopolimer PEDOT-g-PEG mogao bi imati potencijalnu primjenu u polju nosive elektronike.
Abstract (english) Since their discovery, electrically conductive polymers have attracted attention due to their properties such as corrosion resistance, electrical conductivity, and low density. The property of electrical conductivity is made possible by the alternating arrangement of single and double bonds and the introduction of a free charge carrier. One of the main representatives of electrically conductive polymers is poly(3,4-ethylenedioxythiophene) (PEDOT) due to its good chemical stability, biocompatibility, low production cost and electrical conductivity in the semiconductor field. The introduction of poly(ethylene glycol) side branches (PEG) improves stretchability and flexibility due to the formation of non-covalent cross-links by hydrogen bonding, allowing potential application in the field of portable electronics. With additional crosslinking agents, it is possible to achieve full covalent crosslinking, which further increases the extensibility and also improves the resistance to chemicals. The synthesis of the graft copolymer was carried out in four steps. In the first step, the bromofunctionalized thiophene monomer ThBr was synthesized, and in the second step, the macroinitiator PEDOT-Br was synthesized. The graft copolymer PEDOT-g- PEG was then synthesized by grafting PEG side chains onto the PEDOT-Br main chain by atom transfer radical polymerization (ATRP). In the fourth step, ATRP was performed again with an additional crosslinking agent (2-oxo-1,3-dioxolan-4-yl)methyl methacrylate (GCMA) to obtain the covalently crosslinked conducting polymer X-PEDOT-g- PEG. The obtained samples were characterized by nuclear magnetic resonance (NMR), Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The obtained samples were used to prepare inks for inkjet printing on a flexible polyurethane substrate (PU). The printed layers on the substrate were tested for electrical conductivity and mechanical deformability. The results of FTIR and NMR analysis confirm the success of PEDOT-g- PEG synthesis, while DSC analysis shows that the glass transition temperature is below the body temperature (37 °C), which allows the sustainability of the graft copolymer in contact with the skin. The electrical conductivity values are in the range of semiconductors, and a strain of 50% does not cause permanent deformation, while no significant change in electrochemical activity was observed. Based on the overall results, the synthesized graft copolymer PEDOT-g- PEG could have a potential application in the field of wearable electronics.
Keywords
elektrovodljivi polimeri
poli(3 4-etilendioksitiofen)
radikalska polimerizacija prijenosom atoma
poli(etilen-glikol)
inkjet ispis
nosiva elektronika
Keywords (english)
conductive polymers
poly(3 4-ethylenedioxythiophene)
atom transfer radical polymerization
poly(ethylene-glycol)
inkjet print
wearable electronics
Language croatian URN:NBN urn:nbn:hr:149:388266 Project Number: UIP-2019-04-8304 Study programme Title: Materials Science and Engineering - Graduate study Type of resource Text File origin Born digital Access conditions Open access Terms of use Created on 2023-07-27 13:43:12
