Универзитет у Београду, Технолошко-металуршки факултет
Abstract
Heterociklične azo boje sa piridonovim jezgrom predstavljaju značajnu klasu organskih azo boja
jer pokazuju visoki molarni ekstinkcioni koeficijent i dobru postojanost na razne vidove obrade.
Sintezom 2-piridona sa amidnom grupom u položaju 3, i kuplovanjem dobijenog piridona sa
supstituisanim i disupstituisanim diazonijumovim solima dobijene su dvije serije novih azo boja.
Struktura novosintetisanih boja na bazi 6-hidroksi-4-metil-2-okso-1,2-dihidropiridin-3-
karboksamida je potvrđena elementalnom analizom, FT-IR i NMR spektroskopijom. Termička
stabilnost boja je ispitana TG/DTA i DSC metodama, i upoređena sa bojama slične hemijske
strukture. Amidna grupa u strukturi sintetisanih boja dovodi do drugačije uređenosti molekula u
odnosu na jedinjenja ranije poznate strukture, što je predstavljalo veliki izazov za detaljnu analizu
njihove stabilnosti i ponašanja. U ovoj disertaciji je prvi put urađeno detaljno ispitivanje termičke
stabilnosti i određivanje kinetičkih i termodinamičkih parametara termički aktiviranih procesa
degradacije arilazo piridonskih boja. Tehnološki procesi u kojima se azo boje koriste zahtjevaju
povišenu temperaturu pa je termička stabilnost od velikog značaja za implementaciju sintetisanih
boja. Nova saznanja o odnosu elektronske strukture i svojstava sintetisanih boja dobijena su
ispitivanjem uticaja rastvarača različitih svojstava na apsorpcione i fluorescentne spektre boja.
Korelacijom apsorpcionih i fluorescentnih frekvenci izvršena je kvantitativna procjena uticaja
dipolarnosti, polarizabilnosti, proton-donorskih i proton-akceptorskih karakteristika rastvarača na
položaje apsorpcionih i fluorescentnih maksimuma ispitivanih azo boja. Kvantno-hemijski
proračuni su primjenjeni za analizu strukture novosintetisanih boja. DFT metodom je analiziran
uticaj supstituenata i rastvarača, promjene u osnovnom i pobuđenom stanju kao i oblik i energije
graničnih molekulskih orbitala (HOMO, LUMO i Egap). Poređenje eksperimentalnih i izračunatih
vrijednosti strukture i svojstava ispitivanih jedinjenja govori o uspješnosti primjenjenih metoda.
Za arilazo piridonske boje je karakteristična i komercijalno značajna azo-hidrazon tautomerija.
Snimanjem apsorpcionih i fluorescentnih spektara pri različitim pH vrijednostima i primjenom
DFT metode analiziran je uticaj prirode i položaja supstituenata u arilazo komponenti, kao i uticaj
rastvarača na položaj azo-hidrazon ravnoteže kod ovih boja.
Filmovi na bazi poli(vinil-alkohola) i arilazo piridonskih boja su sintetisani u cilju dobijanja novih
dozimetrijskih sistema za detekciju gama zračenja. Dobijeni filmovi su ozračeni različitim dozama
gama zračenja Co60 u INNV, a promjene do kojih je došlo nakon izlaganja γ-zracima praćene su
spektrofotometrijski snimanjem refleksionih spektara ozračenih i neozračenih filmova, kao i FTIR analizom. Prednost polimernih obojenih filmova u odnosu na komercijalno poznate dozimetre
je vizuelno uočavanje promjene boje nakon izlaganja γ-zracima što ih čini jednostavnim za
upotrebu. Promjene boje mogu se objasniti raskidanjem glavnog lanca polimera, nastajanjem
slobodnih radikala i njihovim reakcijama sa molekulom boje.Heterocyclic azo dyes with a pyridone moiety represent a significant class of organic azo dyes
because of its high molar extinction coefficient and good resistance to various types of processing.
Synthesis of 2-pyridone with the amide group in position 3, and coupling of the obtained pyridone
with substituted and disubstituted diazonium salts gave two series of new azo dyes.
The structure of newly synthesized dyes based on 6-hydroxy-4-methyl-2-oxo-1,2-
dihydropyridine-3-carboxamide was confirmed by elemental analysis, FT-IR and NMR
spectroscopy. The thermal stability of the dyes was performed by TG/DTA and DSC methods and
compared with dyes of similar chemical structure. The amide group in the structure of the
synthesized dyes leads to a different arrangement of the molecules in relation to the compounds of
the previously known structure, which posed a great challenge for a detailed analysis of their
stability and behavior.
In this dissertation, for the first time, a detailed examination of thermal stability and determination
of kinetic and thermodynamic parameters of thermally activated degradation processes of arylazo
pyridone dyes was performed. Technological processes in which azo dyes are used require
elevated temperature, so thermal stability is of great importance for the implementation of
synthesized dyes. New knowledge about the relationship between the electronic structure and the
properties of synthesized dyes was obtained by examining the influence of solvents of different
properties on the absorption and fluorescent spectra of dyes. By correlating the absorption and
fluorescent frequencies, a quantitative assessment of the influence of dipolarity, polarizability,
proton-donor and proton-acceptor characteristics of the solvent on the positions of absorption and
fluorescent maxima of the investigated azo dyes was performed. Quantum chemical calculations
were applied to analyze the structure of newly synthesized dyes. The influence of substituents and
solvents, changes in the ground and the excited state, as well as the shape and energy of boundary
molecular orbitals (HOMO, LUMO i Egap), were analyzed by the DFT method. A comparison of
experimental and calculated values of the structure and properties of the tested compounds
indicates the success of the applied methods. Arylazo pyridone dye is characterized by
commercially significant azo-hydrazone tautomerism. The influence of the nature and position of
the substituents in the arylazo component, as well as the influence of solvent properties on the
position of the azo-hydrazone equilibrium in these dyes were analyzed by recording the absorption
and fluorescence spectra at different pH values and applying the DFT method.
Films based on poly(vinyl alcohol) and arylazo pyridone dyes were synthesized in order to obtain
new dosimetric systems for gamma radiation detection. The obtained films were irradiated with
different doses of gamma radiation Co60 in INNV, and the changes that occurred after exposure to
γ-rays were monitored spectrophotometrically by recording the reflection spectra of irradiated and
non-irradiated films, as well as FT-IR analysis. The advantage of polymer colored films over
commercially known dosimeters is the visual detection of color change after exposure to γ-rays
which makes them easy to use. The color changes can be explained by the breaking of the main
polymer chain, the formation of free radicals and their reactions with the dye molecule