Add time:09/25/2019 Source:sciencedirect.com
Solvents can strongly influence the equilibrium between dormant and active species which is involved in 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO)-mediated radical polymerizations. At 110°C, the overall polymerization rate of 3-VINYLPYRIDINE (cas 1121-55-7) in pyridine was logically found lower than that in bulk, due to dilution. However, in ethylene-glycol, the opposite behaviour was observed. According to infrared spectroscopy, this unexpected increase in the overall polymerization rate was attributed to hydrogen bonding between ethylene-glycol and the pyridine rings, which weakens the C–O–N bond of the TEMPO-terminated polymers. Semi-empirical molecular orbital calculations were used to support the FTIR results and to calculate the decrease in the dissociation enthalpy of the polymer–nitroxide bond.
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