Laboratory of Organosilicon and Hydrocarbon Cyclic Compounds (No. 10)

Our research focuses on the development of approaches to selective vinyl-addition polymerization of norbornenes with reactive substituents and the creation based on these polymers high-performance polymers for optoelectronics, membrane gas separation, and other applications. The presence of polar or reactive side-groups in polymers provides the desired properties for advanced materials derived from these polymers. Vinyl-addition (co)polymerization of cycloalkenes leads to polymers with saturated main chains displaying : high glass-transition temperatures high transparency high thermal and chemical stability low free volume enhanced gas permeability. However, vinyl-addition polymerization of cycloalkenes bearing a polar or reactive side-group is usually a challenge. Therefore, our research focuses on the development of approaches to selective vinyl-addition polymerization of norbornenes with reactive substituents and the creation based on these polymers high-performance polymers for optoelectronics, membrane gas separation, and other applications.

Rich synthetic possibilities in norbornene derivatives synthesis afford targeted synthesis of series of monomers with the desired structure. The unique ability to polymerize by different mechanisms leads to the formation of polymers with different structures of the main chain. Thus the researcher has the power to vary both structures of the main and side chain of the polymers. Our group aims to design and synthesize new polymeric materials from norbornene derivatives, which should combine either the high performance of membrane properties, the stability of properties over time, and synthetic availability.

Cycloalkenes can be polymerized according to metathesis (ROMP) and vinyl-addition polymerization. Well-defined catalysts have been successfully developed for ROMP polymerization. These catalysts can catalyze the polymerization of cycloalkenes with various functional groups and in a living manner. Although many different catalysts have been studied for vinyl-addition polymerization of cycloalkenes, there are still no catalysts that have similar characteristics to those developed for ROMP polymerization of cycloalkenes. Therefore, the development of new catalysts for vinyl-addition (co)polymerization of cycloolefins is another challenge. Recently, we have shown that Pd–N-heterocyclic carbene complexes in combination with a borate exhibited extremely high activity and durability: the activity was higher than 100 million g polymer/(mol Pd∙h).

The recent progress in the development of advanced aircraft, racing engines, and military vehicles makes a challenge for seeking the next generation of high-energy-density hydrocarbon fuels. Meanwhile, it is a well-known problem to produce a fuel with a high energy content and suitable low-temperature properties. For example, often high-energy density liquid fuels exhibit high freezing points. Regarding possible increased costs of synthetic high-energy-density liquid fuels, enhanced energetic properties become of crucial importance. The possibility of using the smaller fuel tanks, provided by high volumetric heat of combustion, can give benefits that may outweigh the higher costs of this type of fuel. We have prepared a number of hydrocarbons containing two norbornane moieties or norbornyl and cyclopropyl groups from commercially available 5-vinyl-2-norbonene. The synthesis of these hydrocarbons is simple and it uses well-known tools of organic chemistry like the Diels-Alder reaction and cyclopropanation reaction. The altering of the structure of norbornane-type hydrocarbons allowed us to combine two contradictory properties: high fuel density + low freezing point At the same time, the energy density was noticeably higher than that of the related fuel, JP-10. Altogether these factors make norbornene-based fuels the possible fuel for the future's needs.