The cationic induced oligomerisation of N-Vinylformamide

The cationic induced oligomerisation of N-Vinylformamide

THE MECHANISM OF THE CATIONICALLY INDUCED OLIGOMERIZATION OF N-VINYLAMIDES

PhD Thesis

The topic of the dissertation is the survey of the cationically initiated oligomerization of N-vinylformamide with iodine, bromine, trifluoromethanesulfonic acid, and trifluoromethanesulfonic acid trimethylsilylester as initiators.
Quantum chemical calculations on the conformation and the electron density of N-vinylformamide, as well as on its reaction with electrophiles are presented. The structure of the obtained oligomers is investigated with 1H- and 13C NMR spectroscopy, MALDI-TOF-MS, GPC, IR spectroscopy, thermal decomposition, and quantitative combustion analysis. The influence of the polarity of the solvent, of the initiator, of the reaction temperature, and of the monomer/initiator ratio on yield, degree of polymerization, head group functionality, and chain structures of the obtained oligo(N-vinylformamide) is investigated. In comparison with N-vinylformamide, the ability of N-vinylacetamide, N-methyl-N-vinylformamide, N-methyl-N-vinylacetamide, and N-vinylpyrrolidone in undergoing a cationically induced polymerization to oligomeric products is investigated. The influence of the NH-elimination on the oligomerization process is investigated with N-deutero-N-vinylformamide as monomer and the 2H NMR analysis of the obtained oligomers. From the results, a new mechanism for the oligomerization of N-vinylformamide is proposed and discussed

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