Habilitationen und Dissertationen aus dem IOM
Synthese Stickstoff- und Schwefelhaltiger konjugierter Polymere mittels Cyclopolymerisation von 1,6-Heptadiinen
Dissertation, Universität Leipzig, Fakultät für Chemie und Mineralogie,
The subject of the presented work is the investigation of novel nitrogen and sulphur
containing monomers in the cyclopolymerization. This contains not only the synthesis of
the monomers, but also the structure confirmation of the resulting polymers, the kinetics
of the polymerization and the influence of the hetero-atom on the used initiators,
especially initiators of the Grubbs-type.
The first part of this work deals with substituted N,N-dipropargyle aniline-derivatives that
possess two alkoxid chains in 3- and 4-position of the monomer. These monomers lead
to the synthesis of novel polymers being well soluble in common solvents like chloroform.
The resulting polymers were characterised by well established methods and their
structure was investigated with the help of comparison compounds, 1-(3,4-
Bis(octyloxy)phenyl)-2,5-dihydro-1H-pyrrole for five-membered ring structures and 1-
(3,4-Bis(octyloxy)phenyl)-1,2,3,6-tetrahydropyridine for six-membered ring structures,
respectively. A set of kinetic data of the used initiators could be obtained and the relation
between structure of the initiator, the kinetics and the resulting polymer structure was
discussed. These polymers consist of mixed ring-structures. Using a novel class of
Grubbs-initiators, bearing isocyanate ligands, structures consisting of only fivemembered
ring structures could be synthesized.
In the second part of the work, the synthesis of novel sulphur containing 1,6-heptadiine
monomers for the cyclopolymerisation could be accomplished. This set of monomers
consists of the following parts: first a symmetrical thioether, second the corresponding
sulphoxide and third the sulphone on the one hand and fourth an unsymmetrical
thioether substituted by an alkyl-chain in 2-position on the other hand. Polymers of the
symmetrical thioethers were not soluble, however, novel insights into the mechanism of
Grubbs-type initiated cyclopolymerization and the influence of the sulphur-oxidation have
been reached. For Schrock-type initiators this oxidation seem to play no significant role.
The symmetrical thioether on the other hand leads to the formation of soluble polymers if
Schrock-type initiators are used. Here the influence of the substitution in 2-position of
the 1,6-heptadiine on the polymer solubility was shown. According to the observations
with symmetrical, unoxidized thioethers with Grubbs-type initiators only oligomers were
The influence of the hetero-atoms on Grubbs-initiators used in the cyclopolymerisation of
1,6-Heptadiins is discussed in the third part of the presented work. For nitrogen
containing monomers, the influence of quarternization, the formation of quarternary
anilinium salts, was investigated. For sulphur the influence of the oxidation state on the
metal center of the initiators could be shown.
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