0000000000505558
AUTHOR
Cesar Liberato Petzhold
The anionic copolymerization of 5-(N,N-diisopropylamino)isoprene with styrene
The anionic copolymerization of 5-(N,N-diisopropylamino)isoprene (N,N-diisopropyl-2-vinylallylamine) and styrene initiated with alkyllithium compounds is studied. Copolymers obtained from different compositions are characterized by size-exclusion chromatography (SEC), differential scanning calorimetry and by 1 H NMR and 13 C NMR spectroscopy. Under these conditions the dialkylaminoisoprene, similar to butadiene and isoprene, is more reactive than styrene and is incorporated faster into the polymer backbone. The incomplete conversion of the monomers has been attributed to the formation of intra-or intermolecular complexes between the Li + counterion at the chain end and amino groups. Because…
On the anionic polymerization of dialkylaminoisoprenes, 3. A nuclear magnetic resonance study of the structure of oligo[5-(N,N-diisopropylamino)isoprenyllithium]
The structure of oligo[(5-N,N-diisopropylamino)isoprenyllithium] (number-average degree of polymerization Pn = 1-2) prepared by reaction of alkyllithium with 5-(N,N-diisopropylamino)-isoprene1 in nonpolar (benzene) and polar (tetrahydrofuran) solvents has been studied by 1H and 13C NMR spectroscopy. In tetrahydrofuran, as expected, the negative charge at the terminal chain unit is more delocalized than in benzene and, consequently, the carbon-lithium bond has a more ionic character. In both solvents the living chain end shows a cisoid-4, 1-structure. No cistrans isomerization could be detected. This independence of the carbanion structure of the solvent polarity is explained by the complexa…