Catalysts of Olefin Polymerization
Synthesis of New Multidentate Ligand Families and Novel Chiral Post-Metallocene Complexes as Catalysts of Olefin Polymerization
Tech Area / Field
- CHE-POL/Polymer Chemistry/Chemistry
- CHE-SYN/Basic and Synthetic Chemistry/Chemistry
3 Approved without Funding
INEOS (Organo-Element Compounds), Russia, Moscow
- Institute of Problems of Chemical Physics, Russia, Moscow reg., Chernogolovka\nMoscow State University / Department of Chemistry, Russia, Moscow
- Cornell University / Department of Chemistry and Chemical Biology, USA, NY, Ithaca\nFriedrich-Alexander-University / Institut für Organische Chemie, Germany, Erlangen\nUniversity of Newcastle / School of Natural Sciences, UK, Newcastle upon Tyne\nUniversity of Waterloo, Canada, ON, Waterloo
Project summaryThe problem. Polymer has helped improve living standards of human beings and will continue to do so. There is still a great need for new polymer with novel properties. In addition, higher efficiency catalysts are needed for lowering cost and conserving natural resource and protecting environment. These new catalysts for olefin polymerization will come from the study of new chiral ligands and their complexes, including polynuclear versions.
State of art in the field. After historic Ziegler-Natta catalyst discovery, a great new chapter in polyolefin production was open with the advent of group IV metallocene homogeneous single site catalysts of olefin polymerization. Unfortunately, their high price and high level of IP protection make their broad practical application difficult indeed. Thus no wonder that there is a great flurry of interest in the field of homogeneous catalysis of olefin polymerization with non-metallocene (or post-metallocene) catalysts. A recent review by V.C.Gibson (Chem. Rev., 2003, 103, 283-315) cites almost 500 papers on the subject. A great variety of ligands have been proposed and tested. Still a few chiral versions of such catalysts were designed for the purpose of stereospecific polymerization. In addition, there are a few attempts to use the catalysts to develop heterochain polymerization sets and, to the best of our knowledge, only a few attempts were made to introduce polynuclear complexes as catalysts of olefin polymerization. Finally, combined presence of soft and hard metal ions inside a single catalyst is completely unexplored avenue of research.
The objective of this project:
- To prepare a novel family of new chiral multidentate ligands for making complexes of group 4 metals to form perspective single site catalysts of stereo directed olefin polymerization. To screen them for improved catalyst activity, improved polymerization kinetics, improved selectivity, improved polymer properties, and changes in the polymer molecular weight distribution with possible elaboration of a theoretical approach to design of target oriented generation of catalytic complexes.
- To prepare a novel family of chiral multidentate ligands capable of supporting polynuclear complexes as possible catalysts of olefin polymerization and copolymerization. The mutual orientation in space of the two metal ions may provide possible joint hard and soft metal participation in the same catalytic cycle. Unusual polymers may be produced with the catalysts with particular emphasis on low density polyethylene (LDPE) and thermoplastic elastomeric polypropylene production.
The research team includes:
Nesmeyanov Institute of Organoelement Compounds of Russian Academy of Sciences. One of the leading Russian scientific institutes is very well known all around the world. It includes 39 laboratories and 22 research teams. For the period of 1995-1999 as much as 2000 papers and 12 books were published. Working relationships were established with 150 Universities, Institutes and Industrial Centers both in Russia and abroad. The research areas of interest for the institute include: Chemistry and physics of polymers, Crystallography, Chemistry of organometallic compounds, Catalysts preparation, including nonaparticle type and so on (a brochure on the activities of the institute is available).
Moscow State University, Chemical Faculty is the most important educational chemical establishment of Russia with almost 1200 students studying every year. The educational staff consists of 1200 teachers, including 100 habilitates. The staff is publishing every year 1000 articles. At least 400 grants were awarded to the faculty this year alone. More detailed information can be found at /www.msu.ru/.
The group of Prof. Boris Bulychev is actively involved in synthesis and structure determination of metallocenes of 4-th group other coordination compounds as catalysts of olefin conversions; study of the mechanisms of the catalysis and structure/properties relationship. Prof. B.Bulychev has won a prestigious State Prize for technology elaboration of novel types of fuel components.
The Russian groups are led by Prof. Y. Belokon (PI, INEOS RAS) and Prof. B. Bulychev (MSU) each having more than 200 papers published. Their field of interest includes preparation of new metal complexes, including chiral versions, asymmetric catalysis with chiral complexes and so on.
Polymerization experience of the team is mostly represented by Dr.Bravaya from Institue of Chemical Physics who published more than 100 papers on the subject, including five publications jointly produced with the two other participants.
The role of the collaborators. A great obstacle, hindering the progress of the team research, is almost complete absence polymer analytical equipment in Russia and the difficulties for the newcomers to the field, establishing business and scientific contacts and getting qualified criticism of the obtained scientific results. Collaboration with such world-renowned scientist as Prof. Coates from the USA solves the problem and allows for both efficient analysis of the polymer material obtained and qualified criticism of the scientific approach selected. Prof. Chirik is a well known specialist in the field of organoelement compounds and his experience in the field is of great importance for the synthesis of the future polymerization catalysts.
The project addresses ISTC objectives. Successful implementation of the project, in addition to development of novel technologies and obtaining new knowledge, will allow former Russian military scientists to get involved in peaceful scientific process, enriching both Russia and USA. In case the approach was found to be fruitful, almost limitless perspectives would be open for developing of a new business relationship between the participants. In case of a success and after further developments new efficient technologies of olefin polymerization can be introduced into both Russia and US with high competitive potential for increased production (may be of new material), and new job vacancies open.
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