Aspects of the Synthesis of Poly(styrene-<i>block</i>-isobutylene-<i>block</i>-styrene) by TiCl<sub>4</sub>-Co-initiated Cationic Polymerization in Open Conditions
Miraslau I. Makarevich,
Pavel A. Nikishau,
Ivan A. Berezianko,
Tatiana V. Glushkova,
Maria A. Rezvova,
Evgeny A. Ovcharenko,
Giyjaz E. Bekmukhamedov,
Dmitry G. Yakhvarov,
Sergei V. Kostjuk
Affiliations
Miraslau I. Makarevich
Research Institute for Physical Chemical Problems of the Belarusian State University, 220006 Minsk, Belarus
Pavel A. Nikishau
Research Institute for Physical Chemical Problems of the Belarusian State University, 220006 Minsk, Belarus
Ivan A. Berezianko
Research Institute for Physical Chemical Problems of the Belarusian State University, 220006 Minsk, Belarus
Tatiana V. Glushkova
Research Institute for Complex Issues of Cardiovascular Diseases, 650002 Kemerovo, Russia
Maria A. Rezvova
Research Institute for Complex Issues of Cardiovascular Diseases, 650002 Kemerovo, Russia
Evgeny A. Ovcharenko
Research Institute for Complex Issues of Cardiovascular Diseases, 650002 Kemerovo, Russia
Giyjaz E. Bekmukhamedov
Alexander Butlerov Institute of Chemistry, Kazan Federal University, 420008 Kazan, Russia
Dmitry G. Yakhvarov
Alexander Butlerov Institute of Chemistry, Kazan Federal University, 420008 Kazan, Russia
Sergei V. Kostjuk
Research Institute for Physical Chemical Problems of the Belarusian State University, 220006 Minsk, Belarus
The cationic polymerization of isobutylene and its block copolymerization with styrene using DiCumCl/TiCl4/2,6-lutidine initiating system has been studied in open conditions. It was shown that a higher concentration of proton trap is required in open conditions as compared to the glove box technique in order to have good control over molecular weight and polydispersity. Polyisobutylenes with Mn ≤ 50,000 g mol−1 and low polydispersity (Đ ≤ 1.2) were prepared at [Lu] = 12 mM. The synthesis of poly(styrene-block-isobutylene-block-styrene) triblock copolymer (SIBS) in open conditions required the addition of proton trap into two steps, half at the beginning of the reaction and the second half together with styrene. Following this protocol, a series of triblock copolymers with different length of central polyisobutylene block (from Mn = 20,000 g mol−1 to 50,000 g mol−1) and side polystyrene blocks (Mn = 4000 g mol−1–9000 g mol−1) with low polydispersity (Đ ≤ 1.25) were synthesized. High molecular SIBS (Mn > 50,000 g mol−1) with low polydispersity (Đ Mn > 6000 g mol−1) demonstrated higher tensile strength (~13.5 MPa).
