A new high‐throughput approach to measure copolymerization reactivity ratios using real‐time FTIR monitoring

This paper presents a novel high‐throughput approach to measure copolymerization reactivity ratios from a single experiment using high‐speed real‐time Fourier transform infrared (FTIR) monitoring of the isobutylene/isoprene (IB/IP) system initiated by 2‐chloro‐2,4,4‐trimethyl‐pentane (TMPCl)/TiCl 4 in hexane/methyl chloride (Hx/MeCl) 60:40 v/v solvent at −80 °C. Traditional polymer analysis is severely limited in this system, which is riddled by side reactions. The reactivity ratios calculated by linear (Mayo‐Lewis and Kelen‐Tüdös) methods and by a nonlinear least square (NLLS) method (van Herk algorithm) showed good agreement with r 1 =1.32 and r 2 = 0.74 calculated using Mayr's nucleophilicity scale. Combination of the Kelen‐Tüdös and NLLS methods yielded r 1 = 1.17 ± 0.01 and r 2 = 0.99 ± 0.02. These values agree well with those reported by Thaler et al. but disagree with most reported data.