Generation of novel polymeric materials and catalyst deactivation pathways in polar vinyl monomer insertion copolymerization

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2014
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In the past six years, the longstanding issue of polar vinyl monomer insertion polymerization has seen strong advances. A broad range of monomers, including even vinyl acetate and acrylonitrile, is now amenable to copolymerization with ethylene. Also, a mechanistic understanding has been established which identifies relevant limitations. Thus, coordination of the functional group of free or incorporated polar monomer to the active sites reversibly hinders chain growth and slows down polymerization.
This background raised the following
issues, which are addressed in this thesis. While a range of different copolymers has been characterized on a molecular level, studies of relevant material properties had been lacking. This is a prerequisite for identifying potential applications.

The scope of polar vinyl monomers amenable to insertion polymerization excludes acidic polar groups, although incorporation of such groups is very desirable for e.g. compatibility with inorganic surfaces.

Mechanistically, reversible deactivation pathways are quite well understood. However, the possibility of irreversible deactivation routes had not been considered at all for these copolymerizations, although this would obviously have a decisive impact.

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ISO 690RÜNZI, Thomas, 2014. Generation of novel polymeric materials and catalyst deactivation pathways in polar vinyl monomer insertion copolymerization [Dissertation]. Konstanz: University of Konstanz
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@phdthesis{Runzi2014Gener-28069,
  year={2014},
  title={Generation of novel polymeric materials and catalyst deactivation pathways in polar vinyl monomer insertion copolymerization},
  author={Rünzi, Thomas},
  address={Konstanz},
  school={Universität Konstanz}
}
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    <dcterms:abstract xml:lang="eng">In the past six years, the longstanding issue of polar vinyl monomer insertion polymerization has seen strong advances. A broad range of monomers, including even vinyl acetate and acrylonitrile, is now amenable to copolymerization with ethylene. Also, a mechanistic understanding has been established which identifies relevant limitations. Thus, coordination of the functional group of free or incorporated polar monomer to the active sites reversibly hinders chain growth and slows down polymerization.&lt;br /&gt;This background raised the following&lt;br /&gt;issues, which are addressed in this thesis. While a range of different copolymers has been characterized on a molecular level, studies of relevant material properties had been lacking. This is a prerequisite for identifying potential applications.&lt;br /&gt;&lt;br /&gt;The scope of polar vinyl monomers amenable to insertion polymerization excludes acidic polar groups, although incorporation of such groups is very desirable for e.g. compatibility with inorganic surfaces.&lt;br /&gt;&lt;br /&gt;Mechanistically, reversible deactivation pathways are quite well understood. However, the possibility of irreversible deactivation routes had not been considered at all for these copolymerizations, although this would obviously have a decisive impact.</dcterms:abstract>
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May 9, 2014
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