Abstract
Isobutylene (IB) polymerization kinetics at −80 °C were monitored in real time using mid-infrared ATR-FTIR spectroscopy, with diamond-composite insertion probe and light conduit technology. Monomer concentration as a function of time was obtained by monitoring the absorbance at 887 cm-1 associated with the CH2 wag of IB. Polymerizations were initiated using 5-tert-butyl-1,3-bis(2-chloro-2-propyl)benzene (t-Bu-m-DCC) or 2-chloro-2,4,4-trimethylpentane (TMPCl) in conjunction with TiCl4 co-initiator, in hexane/methyl chloride or methylcyclohexane/methyl chloride (60:40 v/v) cosolvents. Either 2,4-dimethylpyridine (DMP) or 2,6-di-tert-butylpyridine (DTBP) was used as an electron donor (ED). Reaction conditions were [ED] = 2.00 × 10-3 M, [IB]0 = 1.0 M, and [TMPCl] (or 2[t-Bu-m-DCC]) = 2.08 × 10-2 M. Co-initiator concentrations were designed to be less than or equal to the growing chain end concentration and ranged from [TiCl4] = 7.20 × 10-3 to 2.28 × 10-2 M. Steady-state polymerization kinetics were found to b...
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