Catalytic polymerization of cycloolefins and isocyanates with transition metal complexes

Doctoral Dissertation uoadl:2880057 82 Read counter

Unit:
Department of Chemistry
Library of the School of Science
Deposit date:
2019-08-07
Year:
2019
Author:
Chriti Despoina
Dissertation committee:
Χριστιάνα Μητσοπούλου, Καθηγήτρια, Τμήμα Χημείας, Ε.Κ.Π.Α.
Μαρίνος Πιτσικάλης, Καθηγητής, Τμήμα Χημείας, Ε.Κ.Π.Α.
Κωνσταντίνος Μερτής, Ομότιμος Καθηγητής, Τμήμα Χημείας, Ε.Κ.Π.Α.
Κωνσταντίνος Μεθενίτης, Αναπληρωτής Καθηγητής, Τμήμα Χημείας, Ε.Κ.Π.Α.
Παναγιώτης Κυρίτσης, Αναπληρωτής Καθηγητής, Τμήμα Χημείας, Ε.Κ.Π.Α.
Ιωάννης Παπαευσταθίου, Αναπληρωτής Καθηγητής, Τμήμα Χημείας, Ε.Κ.Π.Α.
Πατρίνα Παρασκευοπούλου, Επίκουρη Καθηγήτρια, Τμήμα Χημείας, Ε.Κ.Π.Α.
Original Title:
Catalytic polymerization of cycloolefins and isocyanates with transition metal complexes
Languages:
English
Translated title:
Catalytic polymerization of cycloolefins and isocyanates with transition metal complexes
Summary:
In this thesis two types of metal-mediated polymerization have been studied: (a) metathesis polymerization, including alkyne metathesis polymerization and ring opening metathesis polymerization (ROMP) for the synthesis of unsaturated polymers; and, (b) condensation polymerization for the synthesis of polyurea.
Metathesis polymerization. The kinetics of the polymerization of phenylacetylene, norbornene and some of its derivatives with the catalytic system (Ph4P)2[W2(μ-Br)3Br6]/AgBF4 (1; {W 2.5 W}7+, a΄2e΄3) has been studied. The catalytic system Na[W2(μ-Cl)3Cl4(THF)2]·(THF)3/PA (2; {W 3 W}6+, a΄2e΄4; PA: phenylacetylene) was used for the synthesis of highly crosslinked poly(dicyclopentadiene) (PDCPD) xerogels, which showed extreme swelling. This behavior is unique compared to polymeric and carbon-based adsorbents from the literature, and is directly related to the use of the ditungsten catalyst. Na[W2(μ-Cl)3Cl4(THF)2]·(THF)3/NBD (3; NBD: norbornadiene) was also used as a catalytic system for the synthesis of PDCPD xerogels and aerogels. Those materials are very robust and show high and fast solvent uptake, which renders them excellent candidates for sensors. Finally, those catalytic systems not only provide cost-efficient alternatives to well-established W- and Ru-based catalysts, but also provide polymeric materials with unique properties via facile synthetic routes, rendering them attractive for environmental remediation applications.
Condensation polymerization. The synthesis of polyurea aerogels using transition metal compounds (M: Cr, Fe, Co, Ni, Cu, Mo, W) as catalysts has been studied. The resulting aerogels were doped with metal ions homogeneously throughout their entire network. Those metal-doped aerogels were pyrolyzed providing metal-doped porous carbons.
Main subject category:
Science
Keywords:
aerogels, metal-metal bonds, polyurea, polydicyclopentadiene, ROMP
Index:
Yes
Number of index pages:
12
Contains images:
Yes
Number of references:
279
Number of pages:
251

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