Abstract
Isobutylene (IB) polymerization kinetics were monitored in real time using mid-infrared FTIR-ATR spectroscopy, with a diamond-composite insertion probe and light conduit technology. Polymerization was initiated using the 5-tert-butyl-1,3-bis(2-chloro-2-propyl)benzene (t-Bu-m-DCC)/2,4-dimethylpyridine (DMP)/TiCl4 (1:2:20) system in hexane/methyl chloride (60:40 v/v) cosolvents at −80 °C, with [t-Bu-m-DCC] = 1.90 × 10-3 M and [IB]0 = 1.0 M. Monomer concentration as a function of time was obtained by monitoring the absorbance at 887 cm-1 associated with the CH2 wag of IB. The calculated apparent first-order rate constant of 8.4 × 10-4 s-1 was within 3% of the value determined from traditional gravimetric methods (8.6 × 10-4 s-1) withing the same range of conversion. Inspection of the first-order plot generated from the FTIR data revealed a number of deviations from linearity, which were attributed primarily to a transient rise and subsequent fall in reactor temperature caused by the initial large exotherm of...
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