SYNTHESIS OF WELL DEFINED POLYMERIC/ORGANIC NANOPARTICLES. STUDY OF THEIR EFFECT ON THE PROPERTIES OF NON-LINEAR POLYMERS IN SOLUTION AND BULK

Doctoral Dissertation uoadl:2919677 204 Read counter

Unit:
Department of Chemistry
Library of the School of Science
Deposit date:
2020-07-20
Year:
2020
Author:
PATELIS NIKOLAOS
Dissertation committee:
ΣΑΚΕΛΛΑΡΙΟΥ ΓΕΩΡΓΙΟΣ, ΑΝΑΠΛΗΡΩΤΗΣ ΚΑΘΗΓΗΤΗΣ, ΤΜΗΜΑ ΧΗΜΕΙΑΣ, ΕΚΠΑ
ΠΙΤΣΙΚΑΛΗΣ ΜΑΡΙΝΟΣ, ΚΑΘΗΓΗΤΗΣ, ΤΜΗΜΑ ΧΗΜΕΙΑΣ, ΕΚΠΑ
ΒΛΑΣΣΟΠΟΥΛΟΣ ΔΗΜΗΤΡΙΟΣ, ΚΑΘΗΓΗΤΗΣ, ΤΜΗΜΑ ΕΠΙΣΤΗΜΗΣ ΚΑΙ ΤΕΧΝΟΛΟΓΙΑΣ ΥΛΙΚΩΝ, Π.Κ.
ΙΑΤΡΟΥ ΕΡΜΟΛΑΟΣ, ΚΑΘΗΓΗΤΗΣ, ΤΜΗΜΑ ΧΗΜΕΙΑΣ, ΕΚΠΑ
ΚΥΡΙΤΣΗΣ ΑΠΟΣΤΟΛΟΣ, ΑΝ. ΚΑΘΗΓΗΤΗΣ, ΣΕΜΦΕ, ΕΜΠ
ΑΥΓΕΡΟΠΟΥΛΟΣ ΑΠΟΣΤΟΛΟΣ, ΚΑΘΗΓΗΤΗΣ, ΤΜΕΥ, Π.Ι.
ΑΣΤΕΡΙΟΣ ΠΙΣΠΑΣ, ΕΡΕΥΝΗΤΗΣ Α΄, Ε.Ι.Ε
Original Title:
ΣΥΝΘΕΣΗ ΠΟΛΥΜΕΡΙΚΩΝ/ΟΡΓΑΝΙΚΩΝ ΝΑΝΟΣΩΜΑΤΙΔΙΩΝ ΜΕ ΚΑΛΑ ΚΑΘΟΡΙΣΜΕΝΕΣ ΔΙΑΣΤΑΣΕΙΣ ΚΑΙ ΜΕΛΕΤΗ ΤΗΣ ΕΠΙΔΡΑΣΗΣ ΤΟΥΣ ΣΤΙΣ ΙΔΙΟΤΗΤΕΣ ΜΗ ΓΡΑΜΜΙΚΩΝ ΠΟΛΥΜΕΡΩΝ ΣΕ ΔΙΑΛΥΜΑ ΚΑΙ ΤΗΓΜΑ.
Languages:
Greek
Translated title:
SYNTHESIS OF WELL DEFINED POLYMERIC/ORGANIC NANOPARTICLES. STUDY OF THEIR EFFECT ON THE PROPERTIES OF NON-LINEAR POLYMERS IN SOLUTION AND BULK
Summary:
In this thesis, a series of linear PS-co-PBCB, where PS is polystyrene and PBCB is poly 4-vinylbenzocyclobutene, were synthesized by living radical polymerization (nmp, nitroxide mediated polymerization), as well as five NEW different series of linear PS-b-PBCB, PS-b-PBCB-b-PS by living anionic polymerization techniques. The SCNPs formation were obtained under high dilution and inert atmosphere, via intramolecular dimerization of the benzocyclobutene group at high temperatures. Size exclusion chromatography (SEC), 1H-NMR and dynamic light scattering (DLS) were carried out to verify the SCNPs production. Other experimental techniques, such as differential scanning calorimetry (DSC), broadband dielectric spectroscopy (BDS) and rheology showed a totally different behavior of the nanoparticles polymers versus the linear precursors.
The [4+4] Diels Alder reactions between the 4-VBCBs of the same polymer chain is the reason of the polystyrene nanoparticle size reduction in connection with the linear precursor. Furthermore, this SCNPs formation is the reason of the different physiochemical properties of the final products.
A pure monocyclic polystyrene (c-PS) was synthesized. Atom transfer radical polymerization (ATRP) was employed to prepare well-defined α,ω-functionalized PS, while ring closure “click” reaction was utilized to achieve high coupling efficiency˙ the reaction was carried out in dilute conditions to suppress the inter-chain coupling reaction. The c-PS was purified, from the linear contaminates (“dead” chains during ATRP, unreacted linear PS precursors, dimers) by LCCC fractionation. The c-PS was fully characterized by SEC, 1HNMR, FTIR, DSC, BDS and rheology.
Finally, a series of star-shaped PS homopolymers were synthesized.
The purpose of this thesis is to provide new data on the dynamics of single chain nanostructures and ring polymers in melt, by means of DSC, BDS and rheology techniques.
Main subject category:
Science
Keywords:
4-vinyl benzyl cyclobutene, single chain nanoparticle (SCNP), ring polymers, anionic polymerization, nitroxide-mediated radical polymerization (NMP), atom transfer radical polymerization (ATRP), rheology, differential scanning calorimetry (DSC), broadband dielectric spectroscopy (BDS).
Index:
Yes
Number of index pages:
41
Contains images:
Yes
Number of references:
149
Number of pages:
307
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