In situ monitoring of coordination copolymerization of butadiene and isoprene via ATR-FTIR spectroscopy

FTIR spectroscopy in combination with a diamond tipped attenuated total reflectance (ATR) immersion probe was utilized to study in situ the copolymerization of butadiene (Bd) and isoprene (Ip) with neodymium-based catalyst in hexane. The relationship between the signal intensity of monomer and its concentration was investigated. The kinetic study of copolymerization of Bd and Ip was further conducted, and the monomer reactivity ratios were determined via in situ ATR FTIR. The signal band at 1010 cm−1 was assigned to wagging vibration of Bd and its intensity was proportional to Bd concentration ([Bd]) in the range of 0.46–3.88 mol·L−1. The signal bands at 890 and 989 cm−1 were assigned to wagging vibration of Ip and the signal intensity was also proportional to Ip concentration ([Ip]) in the range of 0.08–4.73 mol·L−1 at 890 cm−1 and 0.08−7.49 mol·L−1 at 989 cm−1, respectively. Thus the signal band at 1010 cm−1 was chosen to monitor Bd concentration and bands at 989 and 890 cm−1 to monitor Ip concentration during the copolymerization, respectively. It was demonstrated that the conversions of Bd and Ip calculated from FTIR data agreed very well with those obtained gravimetrically. The polymerization rates were first order with respect to both [Bd] and [Ip], respectively at different polymerization temperatures. The apparent propagation activation energy for Bd and Ip could be determined to be 54.4 kJ·mol−1 and 57.7 kJ·mol−1, respectively. The monomer reactivity ratios were calculated to be 1.08 for Bd (r Bd) and 0.48 for IP (r Ip) based on FTIR data. The Bd-Ip copolymer products with random sequence could be obtained with only one glass transition temperature.