Homogeneous and heterogeneous catalysts for the synthesis of highly reactive polyisobutylene: discovery, development and perspectives

Abstract

In this article, the current state and future perspectives in the application of complexes of Lewis acids with ethers in the synthesis of highly reactive polyisobutylene (HR PIB) were critically reviewed. The complexes of metal halides with ethers showed good activity and regioselectivity in the synthesis of HR PIB only in polar solvents due to their poor solubility in hydrocarbons. In strong contrast, HR PIB with high exo-olefin end group content was synthesized in non-polar n-hexane using fully soluble in hydrocarbons complexes of alkylaluminum dichlorides as catalysts. The further improvement in the synthesis of HR PIB was achieved using heterogeneous catalysts (acidic ionic liquids or liquid coordination complexes), which provides polyisobutylenes with high exo-olefin end group content in conjunction with low polydispersity.

Graphical Abstract

Keywords:

• Cationic polymerization
• highly reactive polyisobutylene
• complexes of Lewis acids
• homogeneous catalysts
• heterogeneous catalysts

Acknowledgments

The authors grateful to State Program for Scientific Research of Belarus “Chemical processes, reagents and technologies, bioregulators and bioorganic chemistry” (project 2.1.01.03) as well as to BASF SE for financial support.

Additional information

Notes on contributors

Irina V. Vasilenko

Dr. Irina V. Vasilenko is currently a leading researcher at the Research Institute for Physical Chemical Problems of the Belarusian State University (RI PCP BSU). She studied chemistry at the Belarusian State University and received her Ph.D. in 2007 under guidance of Academician of the National Academy of sciences of Belarus Fyodor N. Kaputsky. She joined the group of Prof. Sergei Kostjuk at the RI PCP BSU in 2008. Her research interests include the development of new catalysts for cationic, anionic ring-opening and coordination polymerizations as well as for the synthesis of highly reactive polyisobutylene.

Sergei V. Kostjuk

Sergei Kostjuk has received his Ph.D. degree in polymer chemistry in 2002 from Belarusian State University. In 2002, he joined Research Institute for Physical Chemical Problems and since 2008 he is heading the laboratory of catalysis of polymerization processes in the same Institute. He was promoted to an associated professor in 2012 and a professor in 2021 at the Belarussian State University. In cooperation with BASF SE, he has developed several generations of catalysts for the synthesis of highly reactive polyisobutylene. His research interests encompass the areas of polymer synthesis, catalysis, green and sustainable chemistry, and, recently, stimuli-responsive polymers.