• Elastomers and Composites
• /
• v.44 no.1
• /
• pp.55-62
• /
• 2009

In this study, investigation on the polymerization characteristics of isoprene through nitroxide mediated controlled/"living" radical polymerization techniques was attempted. In the presence of acetol, linear increase of isoprene conversion with time and low polydispersities of the resulting polymers ($M_w/M_n$ < 1.5) were observed, which suggest successful controlled/"living" radical polymerization of isoprene. The microstructure of the resulting polyisoprene was composed of $\sim$ 22% of 3, 4, $\sim$30% of 1, 4-cis and $\sim$ 48% of 1, 4-trans. The optimum polymerization temperature was 145 $^{circ}C$, below which no significant polymerization behavior was observed. Non-cyclic nitroxide, such as di-tert-butyl nitroxide (DTBN) could not mediate the polymerization, whereas cyclic nitroxides (2, 2, 6, 6-tetramethyl-1-peperidine 1-oxyl (TEMPO) and 4-oxo-2, 2, 6, 6-tetramethyl-1-peperidine 1-oxyl (oxoTEMPO)) were successfully employed for the polymerization. However, isoprene dimerization reaction through Diels-Alder process was also observed at the given polymerization condition, which afforded a significant amount of limonene. Isoprene thermal autoinitiation was also possible, which was, however, considered to be not significant under the given polymerization condition.

• Analytical Science and Technology
• /
• v.18 no.3
• /
• pp.194-200
• /
• 2005

The N hyperfine coupling constants ($a_N$) of di-t-butyl nitroxide (DTBN) radicals in water-solvent system were measured with EPR spectroscopy. Various kinds of the solvents with different polarity such as acetone, dimethylsulfoxide (DMSO), methanol, ethanol and 1-propanol were applied and studied. Equilibrium constants for the solvation equilibrium and the solvent parameters ($E_T$, molar transition energy) of various water-solvent system were obtained from the experimental results and are presented. The $a_N$ values were plotted as a function of mole fraction of the solvent. In case of water-DMSO, water-ethanol and water-1-propanol system, slight negative deviations from the straight line were observed. In water-acetone system, the absorption wavelength (${\lambda}$) due to ${\eta}{\rightarrow}{\pi}^{\ast}$ transition increased linearly with the increase of mole fraction of acetone. The relationship between $a_N$ of DTBN and ${\lambda}$ due to ${\eta}{\rightarrow}{\pi}^{\ast}$ transition in water-acetone and water-DMSO system was examined. It was found that the electronic structure of the nitroxide radicals is stablized from the fact that the N hyperfine coupling constants of DTBN radicals are greatly unaffected in the environment of water-solvent system.