One of the key directions of our investigations is the rational design of effective catalysts for vinyl-addition polymerization (VAP) of various norbornene derivatives. In the last 5 years, our team together with the colleagues from TIPS RAS managed to significantly expand the scope of research on Pd-catalysts for VAP. Sequential optimization of the structures of NHC-Pd complexes led to the formation of ultra-active catalytst that made the control of vinyl-addition polymerization much more accessible. An understanding of key principles of the mechanism of polymerization led to attempts of development of single-component Pd catalytst for VAP.

In the current review published in ChemCatChem, the head of our lab Maxim Bermeshev together with Eugenia Bermesheva discussed the recent advances in this area and poses key directions for the upcoming development of such catalysts.

Definitely must-read. The review has open an access option.

Recently our team published a research paper on another approach to the synthesis of silicon-containing polynorbornenes using post-modification of poly(5-ethylydene)-2-norbornene. The results were presented in Polymer Chemistry.

The main idea is a straightforward and efficient method for synthesizing various silicon-containing vinyl-addition polynorbornenes by hydrosilylation of side chains in a parent polymer containing vinyl groups. A huge effort was put into the search for efficient catalysts for hydrosilylation. Traditional Karstedt's catalysts exhibited high activity, but provided insoluble products. In turn, the application of less active (NHC)Pt catalytst led to the formation of soluble products. Optimizing the catalyst's structure made it possible to find the most efficient (NHC)Pt-catalyst among the studied complexes.

This catalyst allowed us to reach high selectivities and conversions (>90%) of vinyl groups in PVNB.

Our huge congratulations to Alyona Wozniak, Evgenia Bermesheva and the whole team!

December 7th became another significant day for our lab. Vsevolod Zhigarev presented his fundamental work on synthesis and post-modification of silicon-containing poly(tricyclodecadienes). As a result of the presentation, Vsevolod defended his PhD thesis.

The realization of a promising idea underlying in the basis of the Vsevolod's work has turned out to bring a lot of challenges. We suffice to say each of the results obtained was achieved through hard work. That makes the outcome even more valuable. The presentation went well as Vsevolod managed to keep confidence and calmness during his tals. Our warm congratulations to Vsevolod!

You can also check the most significant publications on the topic in Polymers, European Polymer Journal and Polymer Science Series C.

Winter came to Moscow with a huge snowstorm last weekend. So the first monday of winter season was full of charming impressions.

It's time for a final push to finish the year strong. One of the keys to the strength is a monday delivery of liquid nitrogen to the lab. Our team can do that despite any weather surprises.

Enjoy the winter and it's upcoming weekends!

Our researchers have found a new way to involve bromo-substituted norbornenes in vinyl-addition polymerization.

It was presiously shown that bromo-substituted norbornenes are inactive in homopolymerization reactions. Earlier the related polymers were synthesized via copolymerization with active norbornene-type monomers.

In the present study norbornene lab group successfully studied the reactivity of bromine-containing norborenes in the vinyl-addition polymerization. A series of the monomers with varied spacing between the norbornene backbone and the bromine atom were involved in the polymerization. One of the keys to success was the application of one- and three-component Pd-based systems bearing N-heterocyclic carbene ligands.

These polymers can subsequently be used as precursors for the production of anion-exchange membranes with a large proportion of ionogenic groups.

The related results were published in Polymers.

On November 13-17 th, three members of Norbornene lab presented TIPS RAS on the "Modern problems of polymer science" conference. The conference took place in the historical building of Russian academy of sciences in Saint-Petersburgh.

Gleb Karpov presented preliminary results on new palladium catalysts for polymerization on poster session. Alexander Morontsev attended the conference with a poster presentation on metathesis olygomerization of 5-n-butylnorbornene in the presence of dimethylmaleate. Vsevolod Stepanyants had his debut with oral presentation on tandem process of metathesis polymerization-hydrogenation of cyclic oligomers. Young Vsevolod did his best preparing the talk and himself (check his suit). Huge congratulations!

Despite Saint-Petersburgh is believed to be a capital of dark and grey vibes in Russia, we spent a fun time at the city. Many thanks to the organizers for a warm welcome.

On October 8-12th, Maxim, Dmitry and Peter presented their recent works on the development of polymers and membrane materials based on organosilicon monomers at the 9-th Bakeev all-Russian conference for young scientists "Macromolecular nanoobjects and polymer composites".

The conference took place at Tula State Pedagogical University named by Lev Tolstoy, who was a famous Russian writer. Couldn't miss the opportunity of taking a photo with Tolstoy's charachter.

The recent results obtained in our lab were presented in the conference "Baikal Readings 2023"by Maxim B. and Jane B. The conference took place near the pearl of the world – Lake Baikal.

Jane gave a short report on the recent advances in development of single-component catalysts for vinyl-addition polymerization of norbornene derivatives. Maxim presented a traditional introducing lecture on polymeric materials based on norbornene-type monomers.

Thanks to Organizing Committee for the excellent organization and the nice venue!

Maxim Bermeshev and Jane Bermesheva took part in the conference "Ideas and Legacy of A.E. Favorsky in Organic Chemistry", which was held in Saint Petersburg, Russia.

Maxim gave an invited lecture on the targeted design of polymeric membrane materials derived from norbornenes.

Jane gave an oral talk describing recent advances the group has made toward the development of single-component catalysts for vinyl-addition polymerization. Fresh results of our team in this direction were recently published in ACS Catalysis. Moreover, we're preparing a review on the topic of Jane's talk.

Hopefully next time we'll be able to announce the upcoming lectures of our leading specialists.

On May 22-27th, Artem Lunin and Alyona Wozniak took part in the conference "Ion Transport in Organic and Inorganic Membranes".

Artem gave an oral talk devoted to polymeric ionic liquids based on vinyl-addition homo- and copolymers of 5-hexyl-2-norbornene and 5-(4-bromobutyl)norbornene. Various physicochemical properties of the synthesized polymers were studied. This work is a part of Artem's graduate work that's planned to be defended next summer. Moreover, that was the first oral talk for Artem on such conference. Congrats on well-prepared presentation and confident report!

Alyona presented her results on anion-exchange membranes based on quaternized vinyl-addition poly(5-vinyl-2-norbornene). This work is an extension of her Ph.D thesis defended last year dedicated to synthesis post-modification of vinyl-addition poly(5-alkylidene-2-norbornene) derivatives. It was shown that increasing the molar fraction of hydrophilic moities in copolymer leads to a significant increase in conductivity. The results were obtained in cooperation with the colleagues from Kurnakov Institute of General and Inorganic Chemistry.

Norbornene lab received funding from the Russian Science Foundation to support our work in the development of Pd-based catalytic systems for norbornene/ethylene copolymerization. That's the first project to be led by Gleb Karpov. Congrats!

Thank you to RSF for your generous support!

Dmitry Alentiev attended an annual scientific-practical conference "New polymer composites – Mikitaev's Readings" held in Kabardino-Balkaria (Russia), near Elbrus.

Dmitry gave an oral lecture on the latest advances in designing membrane materials based on vinyl-addition polynorbornenes with oxygen-containing substituents. In the lecture, he summarized the relationships between the chemical structure of these polymers and their gas transport properties found in the recent studies carried out by Norbornene lab in collaboration with the membrane center of TIPS RAS.

Noteworthy, Dmitry attends the conference for the second year in a row. It looks like a solid recommendation by one of the key team members.

Long term effort of our team led to a new publication. Our article on the development of nadimides-based vinyl-addition polymers as gas separation membranes for CO2-removal was recently published in Journal of Membrane Science.

A series of racemic and chiral nadimides synthesized by Ivan Nazarov were obtained and characterized. A joint effort of our colleagues from Lab#22 (Maxim Topchiy, Andrey Asachenko) and our specialists on catalysis And polymerization (Ekaterina Medentseva, Anna Khrychikova, Evgeniya Bermesheva, Alyona Wozniak) resulted in series of new polymeric materials that have previuosly been out of reach. Thanks to TIPS RAS Membrane Center new correlations between polymer structure and its membrane properties were found. Particularly, VAP polynorbornene with fluoroaryl-groups in imides moieties exhibited the combination of high CO₂ permeability with attractive CO₂/N₂ and CO₂/CH₄ selectivities.

Find out more in the full text available in the Journal of Membrane Science.

Congratulations to the whole team!

Nothing serious. Just a new poster portraying our team members as cartoon characters :)
You might've noticed familiar faces along with a new ones. That means we have new members to introduce. Check out the updates soon!

Credits to Fedor Andreyanov for design and patience. Yes, that work demanded loads of version to please every member :)

We have just received a grant from Russian Science Foundation to investigate polymers based on chiral norbornenes. By the way, a portion of interesting results on the related topic is going to be out soon in the Journal of Membrane Science.

Thanks RSF for supporting our research!

On March 31st, several members of our lab visited Harz Labs company, the leading 3D printing materials company in Russia.

Thanks to Dr. Pavel Chapala for the invitation and for hosting the visit!

Lab 10 received funding from Russian Science Foundation (RSF) to support our work in the development of new synthetic motor oils.

Thanks to RSF for your generous support!

Our team has worked long on new type of polynorbornenes bearing rigid carbocyclic substituents in side chains. The results were published in Polymer journal.

Four sets of polymers from norbornene-type monomers with various carbocyclic groups were prepared to perform the structure-property study and to evaluate the effect of main- and side-chains on the porosity of resultant polymers.The obtained polymers exhibited large BET surface areas (up to 740 m²/g), while CO₂ and H₂ uptake reached 3.0 and 0.18 mmol/g, correspondingly. The combination of comparatively simple synthesis, high porosity and solubility in organic solvents can be considered as a key advantage of the synthesized polymers.

We're preparing another set of results on the topic. In the meantime we congratulate Maxim Zotkin on his first research paper!

On the 9th February, on the day of Russian Sciences, Dmitry Alentiev and Alyona Wozniak from our lab together with our colleague Andrey Asachenko were given the Prize of Moscow government.

The award was presented for the development of approaches to the synthesis of functional polynorbornenes, promising materials for membrane gas separation. That has become the result of the last 5 years of dedication to organometalic chemistry, catalysis and polymerization procedures. NHC-Pd complexes developed by Andrey Asachenko and his team made synthesis of new specific polynorbornenes simplier than ever. Alyona Wozniak's effort was focused on the assesment of catalytic activity of Pd-NHC complexes in norbornenes polymerization. A wide set of polymers based on 5-ethylydene-2-norbornene and other bifunctional monomers was obtained due to extraordinary selectivity of the new catalysts. That opened the way to a new series of polynorbornenes synthesized as a result of various post-modifications. With the help of such effective catalysts Dmitry Alentiev managed to obrain new silicon containing polynorbornenes being one of the attractive membrane materials to date.

We're proud of our colleagues.

Our team has developed new generation of single component catalysts for vinyl-addition polymerization of norbornenes. The paper was published in ACS Catalysis.

We have shown that cationic Pd-complexes with N-heterocyclic carbene ligands and weak coordinating anion ligands are highly efficient single-component catalysts for polymerization of both norbornene and various substituted norbornenes. These complexes, being stable in the solid state and in solutions, have exhibited several important features as VAP catalysts. They are capable of catalyzing VAP of norbornenes in air and are tolerant to functional groups. The complexes have shown high catalytic activity and have allowed polymerizing monomers at very low catalyst loadings, as low as 2 ppm.

Read more in the full paper in ACS Catalysis

The work was supported by the Russian Science Foundation and the State Program of TIPS RAS.

Last week Dmitriy, Fedor, Max and Andrey attended a major meeting of specialists in membrane science "Membranes-2022". The conference took place in Tula region on 26-29th September.

Dmitry had oral presentation about promising membrane materials for CO2 separation based on vinyl/addition polynorbornenes bearing ester fragments in side chain. The presentation was based on Dmitry's recent paper in Journal of Membrane science.

Max also had oral presentation. His recent progress in synthesis of norbornene-based polymers with carbocyclic substituents in side chain gain much attention. The material of Max's presentation is going to be published soon.

Fedor was lucky to have a poster presentation (which was completed successfully few hours before the departure to the conference). His significant effort on membrane materials based on organosilicon derivatives of 5-norbornene-2-methanol was recently published in Polymer.

Andrey presented the results he obtained in the Kurnakov Institute of General and inorganic chemistry during his course work.

We believe the guys had a good time, as the picture shows :)

On June 17th our team gathered all together for the annual seminar. Main focus of the meeting laid in the recent research progress of our young collaborators.

Marina Guseva and her student Petr presented new results on exo-selective synthesis of norbornene derivatives via hydrosylilation reaction. Major questions touched the catalysts choice and possible mechanism of the reaction. Fedor Andreyanov and his younger colleague Artem reported synthesis and properties of new polymers derived from 5-norbornene-2-methanol. Maxim Zotkin shared his progress in the synthesis of norbornene derivatives bearing carbocyclic substituents - promising class of membrane materials. Ivan Nazarov and his students presented huge synthetical work on optically active norbornene derivatives and their polymerization in the presence of optically active catalysts. Vsevolod Zhigarev completed the presenters team with recent results on olefin cross metathesis reaction and synthesis of multiblock copolymers.

We're proud of our young researchers and believe you'll see the results of their effort in upcoming papers.

On May 19th, our team member Gleb Karpov presented his research "Synthesis of fluorine-containing norbornene derivatives and its polymerization". The main focus of the investigation was put in the synthesis of tricyclononenes bearing different organofluorune fragments. The challenging task of obtaining soluble high-molecular weight metathesis polymers was successfully reached. Classical step to the synthesis of vinyl/addition fluoropolymers wasn't that easy in this case though. However, a new vinyl/addition polynorbornene bearing perfluorophenyl groups in side chains was prepared. Moreover, the search for active Pd-based catalytic systems for the polymerization led Gleb to revealing a new type of catalysts based on Pd(0) complexes activated by organic cocatalyst. New approach inspired by organic Pd-catalyzed coupling reaction of aryl (pseudo)halides consisted a solid part of PhD thesis presented by Gleb. Gas transport and dielectric properties of the polymers were studied. The analysis of the data obtained helped us establish new correlations between polymer structure and its properties.

Well done Gleb!