rus
Issue #2/2016
A.Muzafarov
New horizons of chemistry of organoelement compounds: INEOS is ready to technological Breakthrough
New horizons of chemistry of organoelement compounds: INEOS is ready to technological Breakthrough
Aziz M. Muzafarov, Director of the Institute of Organoelement Compounds of RAS (INEOS) and Member of the Russian Academy of Sciences tells:
Institute of Organoelement Compounds of RAS named after A.N.Nesmeyanov (INEOS) had been targeted at fundamental studies in one of the most promising and dynamically developing branches of organoelement chemistry ever since its foundation in 1954. However, scientists never restricted their research efforts by pure theory; they implemented obtained results in mass production processes and products in demand at variety of markets, from medicine, textile fabrics, and food to fine chemicals and defense-related components.
Emerging 21st century had initiated the next, fourth, scientific and technical revolution, including new materials with unique properties, amazing production processes, and, as a consequence, the need in a principal reconstruction of many industries. Chemistry of organoelement compounds is among those scientific and technical sciences, which largely determine progress in up-to date industrial technologies. How do scientists of INEOS respond to these challenges? This was told to us by Aziz Mansurovich Muzafarov, the famous specialist in the field of organosilicon compounds, director of INEOS, and full member of RAS.
Aziz Mansurovich, INEOS is one of the world and Russia leading academic research centers in the field of organoelement chemistry. What are the most important problems facing the Institute at present?
INEOS is really one of world’s leading research centers in the field of basic research organoelement chemistry. Its specifics and main research areas were defined by the founder of INEOS, President of the USSR Academy of Sciences, Alexander Nikolayevich Nesmeyanov. It is commonly believed at present that science is interdisciplinary, that discoveries are made at the junction of sciences. Meanwhile, academician Nesmeyanov said about these junctions as points of accelerated scientific and technological growth as far back as 60 years ago. Moreover, properly speaking, he founded our Institute just as cross-disciplinary project at the interface of organic and inorganic chemistry, where rapid development had been expected.
In fact, INEOS was the first institution of this kind. Although it was intended primarily for public researches, the Institute had allowed a number of “closed” academicians to conduct basic studies and win a worldwide recognition. In this view, the Institute had been equipped with the latest state-of-the-art facilities including a very reasonably arranged scientific instrument park, workshop, pilot sets, and the conference hall, which even now allows to hold international conferences.
A lot has happened since those days. The Institute has a quite incredible service record and history. It is enough to say that INEOS was the very same place where the beautiful polyhedral structures such as carboranes and metallasiloxane compounds were discovered. Commonly known products that had become the pride of Soviet chemistry of those times such as an artificial red and black caviar, popular synthetic textile fiber Lavsan (the word “lavsan” is derivative from the name of our laboratory for macromolecular compounds, in Russian “Laboratoriya Vysokomolekulyarnykh Soyedineniy”, which had developed this material), etc. had been created here. The list of similar innovations that were later used in wide range of industries is very long. Nevertheless, in spite of those successes, INEOS never planned to transform into an applied institution. We always were and we are aimed at the development of fundamental concepts in chemistry of main classes of organoelement compounds such as organometallic, organoboron, organosilicon, organophosphorus, and organofluoric compounds.
The valuable experience gained by the Institute over the past years has allowed creating a number of new scientific schools that uniquely combined organic, organoelement, coordination, and physical chemistry as well as the chemistry of macromolecular compounds and natural biologically active substances. However, some blurring of initial research directions took place as a result. Demand for organoelement compounds has risen sharply in many industries, and at some point, our research increasingly become concentrated in the adjacent application areas. While the Institute had started in 1954 with a dozen of laboratories, their number rose up to 54 by 2010. However, today basic researches in the field of organoelement chemistry are imperative of our era.
We had discussed the situation at one of sessions of INEOS Scientific Council and concluded that we needed to concentrate efforts and go back to fundamental principles, that is, to advancement in initial research directions. We decided that only 25 laboratories plus 10 interim research groups are enough for this purpose. The concept of interim research groups is adopted as basic structural principle in virtually all scientific institutes (at least institutes of RAS Division of Chemistry). It permits to avoid disintegration of research units and multiplication of research directions inside the units. At the same time, emerging specific promising ideas are studied by research groups that are formed only on a temporary basis. Researchers in a group have three years to prove or reject the proposed idea. Of course, nobody requires a discovery from such group since a scientific knowledge is the matter of high priority here and either positive or negative result are of equal importance. However, if an idea was proved true, and the group managed to develop it during that time, then this group can apply for foundation of new laboratory. Otherwise, nothing bad happens, the scientists will return to their previous working positions in order for preparing to next attempt. Such organizational approach allows Institute, on the one hand, to follow the main research directions associated with main classes of organoelement compounds, and, on the other hand, to conduct pioneer researches in the frontier areas.
Of course, such reorganization hardly can solve all problems. In particular, one acute issue of today is the revival of several lost directions that had been successfully developed in INEOS in the past and are obviously in demand both today and in the future. Unfortunately, we have lost a number of scientific schools. A typical example is formerly very strong laboratory of organoaluminum compounds, which are the components, in particular, of the very important catalytic systems and propellants. Another example is researches of polyphosphazenes belonging to one of the unique types of polymers, which were synthesized in INEOS at the highest unique level. However, in the past years of economic reconstruction, normal funding was discontinued while demand for some innovations was virtually ceased. Consequently, progress has stopped, and survival began. Many researchers left the Institute, some died, others changed specialty. In absence of leaders, these directions stopped development.
Very large efforts and investments are required now to restore appropriate levels in these fields. It is necessary, however, to do this, because the main purpose of INEOS, as we see it today, is to rise up to a new level of research, thus make a breakthrough, and create a scientific basis for new generations of technologies. This task requires concentration of research efforts on the fundamental issues of chemistry of organoelement compounds, i.e. on problems that were the initial purpose of INEOS.
I would like to underline once more that this is imperative of our era. If we want to stay members of the highly developed countries club, we need to rebuild the Russian industry in jump-like manner as dictated by the breakthrough strategy. However, technological breakthrough rarely arises due to inspiration only; it should be performed on a strong fundamental basis. Therefore, the deeper we will be able to work out a certain direction, the more probable a breakthrough will be.
What technological breakthroughs in the field of organoelement compounds do you expect?
Let us look at the direction closest to me – silicones. Today, processes of third generation are commonly used for their preparation. The first generation, from which all it began, was based on the reaction of tetrachlorosilane conversion into esters of orthosilicic acid. Then the time of the organomagnesium synthesis based on Grignard reagents had come. Main types of silicone products were produced using just second-generation processes. Then there was another technological revolution caused by the discovery of the chlorosilane direct synthesis method enabled to obtain the basic silicone monomer, dimethyldichlorosilane, directly from silicon and methyl chloride in a single step reaction. The silicones market had responded immediately since the companies that largely invested into organomagnesium synthesis turned out to be losers. Economics of production based on old or new processes had been proved quite different. To use new processes, it was necessary to purchase licenses from patent holders.
It should be noted here that silicones represent the area of industrial production owned by only highly developed countries. In fact, it was club of five World Powers. The Soviet Union was a member of this club absolutely legitimately, because in 40-50-s it built its own industry of these substances production based on the third-generation technologies. We produced the entire wide range of silicone products, from rubber and varnishes to adhesives and glues. From the methodological point of view, it was a completely original development of Soviet chemical engineers. Nobody sold us patents in those times.
The new industry has been created by efforts of team of scientists headed by academician Kuzma Andrianovich Andrianov, one of the founding fathers of organosilicon chemistry as a whole. I would like to emphasize that the complete system was created, designed to meet the demand for silicones primarily in the aviation and space engineering. The scientific support was provided by a number of specialized laboratories, including the laboratory for organosilicon compounds of our institute. Qualified specialists for the industry had been trained by the faculty headed by academician K. A. Andrianov at Moscow Institute of Fine Chemical Technology named after M. V. Lomonosov. Finally, of course, the bedrock of the industry was the creation of the branch technological institute GNIIChTEOS (State Research Institute for Chemistry and Technology of Organoelement Compounds) owing to great efforts made by K. A. Andrianov. GNIIChTEOS was a kind of technological center, in which experts from various academic and industrial institutions were collected. No processes could be implemented at production plants without debugging and trials in GNIIChTEOS. The production plants had been constructed simultaneously. There were five such production plants, each being specialized in specific products.
Thus, a strong scientific and industrial foundation, from basic research to technological development and production, was put into base of the Soviet silicone full-cycle production. Moreover, it was a well-managed centralized system. This system broke down when the coordinating body, USSR State Committee on Science and Technology, which linked the production practice with academic developments, disappeared. In a certain sense, academic institutions in that time found themselves in vacuum while productive enterprises stopped production because they were strongly centralized and they did not know how to work in the market. For this reason, industrial production of silicones in former USSR, which reached about 100 thousand tons in 1991, was substituted for import of silicones, which reached almost the same amount, 90 thousand tons, in 2010. It means that silicones market has remained, but it is now not ours. That is why there is no sense just to restore and reproduce what was done before.
Our industry seems to be lucky compared with others: it succeeded to preserve, although partly, manufacturing capabilities and preclude ruination of GNIIChTEOS (now this institute is attached to the holding “RT-Chemcomposite” being part of the Rostec State Corporation). Now closed-cycle production of silicone monomers is restored at the Kazan factory of synthetic rubber for the first time in many years. This enterprise will operate using old, well-known processes, but it is evident now that its capacity is not enough to control entire market. Nevertheless, the good news is that this enterprise will allow keeping technological culture and ability to design and implement innovations as well as to solve some problems of import substitution and import independence in defense industries.
However, in order to regain a leading position in the production of silicones, Russia needs a transition from the existing technologies of their production to the new, fourth-generation, processes, which will create a real advantage over potential competitors. I say ‘potential’ because we are not real competitors yet.
What principles will be put into base of the fourth generation of silicone production technology? Why do you think that the domestic industry has the ability to implement them before the others?
The fourth generation will be based on chemical reactions that do not use chlorine. At present, the process flowchart for producing these substances (third generation) is arranged as follows. First, chlorosilanes are synthesized. Then they are converted into the siloxane intermediates and products for further processing using processes of hydrolytic polycondensation. We have opened novel catalytic processes based on alkoxysilanes rather than chlorosilanes, which allow rebuilding the entire silicone chemistry by excluding any chlorine derivatives from it. Now alkoxysilanes can be obtained directly from alcohols and silicon in one-step. This provides benefits in almost all stages of the silicones production flowchart. Besides, production of alkoxysilanes by direct synthesis ensures a number of additional advantages rather than being simply more effective. First, chlorosilanes are not far away from chemical warfare agents and hence require great care in handling unlike alkoxysilanes, which can be produced in virtually any environment.
Large companies leverage chlorosilanes in their manufacturing cycles since just chlorosilanes make it easier to command at the market. After all, very large investments are required to launch such production including recycling technologies. Of course, today processes of third generation are advanced up to perfection, so that columns of direct synthesis somewhere in Wales may well be installed as closely as 300 meters from a school, owing to ideal process control and strictly guaranteed safety. Nevertheless, chlorine is chlorine, and if you make use of chlorinated derivatives to produce monomers, then you must recycle them afterwards.
However, it looks quite different when you switch to alkoxysilanes: only very lazy may say that it is too hard for him to recycle these substances. Therefore, it is not simply switching to a next process generation, but qualitatively very different perception of the silicone production process. In fact, it is a very different economy, in which silicones cease to be very specific, difficult to manufacture products.
Here many opportunities open just for domestic enterprises. Firstly, the whole world is now working on the technological groundwork of 20–30 years old. Naturally, the companies engaged in the production of silicones closely monitor all innovations around the world. Nevertheless, even if a technological breakthrough took place there, nobody will immediately begin to close operating plants and switch to a new technology, at least as long as he or she will compensate all previous investments. This circumstance gives us a time handicap of 3–5 years, of course, if we are able to quickly create new technologies. It is why research in this direction is one of our priorities. We are ready to production of certain alkoxysilane types, but a lot of work is still to be fulfilled to implement all required product line.
In general, silicone products have one huge advantage – they are fully recyclable. We can fully rework them into initial materials, that is, decompose a piece of silicone rubber onto components (monomers and filler) and then turn them again into the same rubber. Such deep reworking in combination with the chlorine-free process make silicones unique and promising products.
Moreover, we can already speak about the fifth generation of processes, when it will be possible to produce silicones directly from silicon oxide – silica (simply stated, quartz sand) rather than pure silicon by attaching organics directly to it. In other words, we can eliminate one more stage, recovery of silicon from the sand, out of the production process. Such attempts have already been made, but so far, they are still those swallows that do not make spring. Nevertheless, they determine a strategic research vector.
In general, we clearly understand what you need to do in the field of silicone chemistry. Of course, many interesting things can be done within paradigm of the third generation as well, but there hardly will be a breakthrough. Nevertheless, the breakthrough is imperative, as it was explained above.
In which directions is it supposed to develop chemistry and technology of other main classes of organoelement compounds?
Each of these classes of substances is very specific, and hence strategies of research development are very different from each other. In some cases, we are already seeing the following process stage, while in other cases, only progressive accumulation of knowledge and technological evolution are observable. However, in all cases we can point out the problems that need to be addressed first.
For example, situation in the area of organophosphorus compounds is very similar to the area of organosilicon compounds: in both areas, there is the problem of transition to chlorine-free productive methods. Organophosphorus chemists at present have advanced in the process technology much further than their colleagues, organosilicon chemists. At the same time, organophosphorus chemists have a very acute problem with the industrial implementation. The country has lost a great share of both technological groundwork and organophosphorus compounds production facilities. There is no even an institute similar to GNIIChTEOS, which could be responsible for implementation of new methods in manufacturing technology. At present, the only available option seems to be in collaboration with very powerful corporations that produce phosphate fertilizers. We must try to convince them of the need to diversify their business.
In general, progress in the fields of organoboron and organofluoric chemistry has the form of gradual evolution. Preparative methods and productive processes for both classes of compounds are well studied and advanced, although the problem of synthesis simplification and conditions optimization always stays urgent. On the other hand, range of applications for both classes of substances is very wide; the demand for them is high, whereas unique properties allow looking for new application areas.
In particular, main trend in chemistry of organoboron compounds in INEOS consists in preparation of carboranes, which first were synthesized by us simultaneously with the Americans in the early 1960s. Carboranes are molecules with a specific structure built of carbon, boron, and hydrogen atoms. They have appearance of spatially cyclic macromolecules (macrocycles) very similar to fullerenes and possess many interesting features. A propos, fullerenes were first calculated by theorists of our institute as well; authors named them “footballens” because of their resemblance to a soccer-ball. Carboranes find many various applications from fuels additives and components of adhesives to drugs used in neutron capture therapy of cancer. Carborane-based liquids have very unusual rheological properties that are promising for future use.
In contrast, chemistry of organofluorine compounds is the chemistry of hydrophobic and superhydrophobic substances. All neutral super oil-resistant coatings and rubbers are based on organofluorines. “Blue Blood” (artificial blood substitute based on perfluorocarbons) is also organofluorines, which are remarkable also for huge oxygen solubility. Experiments are known, in which a mouse fully immersed in the perfluorocarbon liquid could quietly “breathe”during a very long time.
Another important area is preparation of new fluorinated hydrophobisators with reactive silicon-containing functional groups. Such substances easily bind to any surface and therefore are attractive for application as highly adhesive coatings. The researches aimed at organofluorines application in supercritical media have a no less strong potential. They play a great role in detoxification of soils with excessive herbicides content. A special INEOS-initiated program of the Russian Foundation for Basic Research focused on this research area was even started in 2015.
The primary task facing the Institute in the field of organofluorine compounds consists in transition from experimentation to industry, from retort to productive processes. Fortunately, here we have someone to rely on. Our partner in technological development in fact grown out of our Institute is the Research & Production Association “P & M-Invest”, which produces organofluoric reagents.
Once more INEOS general direction from “Nesmeyanov’s bunch” is related to chemistry of organometallic compounds. Such compounds are in demand by a variety of industries including the defense ones, where, in particular, they are used as fuel combustion regulators. Certain prospects are connected also with application of organometallic compounds in catalytic reactions.
Organometallic compounds are actively used to produce drugs in the fine organic synthesis, too. Moreover, certain organometallic compounds are drugs themselves. A striking example is the iron-containing compound ferrocene, which was studied intensively still during the life of academician A. N. Nesmeyanov. The pharmaceutical composition ferroceron was developed based on this substance.
Among promising research directions I would like to note lanthanide-based organometallic compounds. These rare earth elements are not so rare and expensive, as many think; they are sincerely practicable.
Generally speaking, almost all basic researches that are “praise rather than pudding”, are valuable precisely in that they lead to a true understanding of what and how is happening in chemical systems and in fact are themselves the door to the future. Often researches yield nothing of what originally expected, but sometimes the unexpected result determines the future development direction.
Can you provide some example of such unexpected, opening new horizons, research result?
Yes, of course. There is one amazing class of substances among polysiloxanes, which have a very eloquent name “dendrimers”, in other words, polymers with a tree-like, fractal structure. At the same time, these molecules have nearly circular shape. It is hard to propose a higher technology in chemistry. The compounds are very interesting in relation to both structure and properties. In this view, they can be considered as either macromolecules or almost spherical particles. Due to this unique combination of properties, dendrimers are now increasingly used in biological studies, medicine, catalytic and photochemical processes. The number of promising application areas is permanently growing.
Indeed, as A. M. Butlerov taught, the uniqueness of structure predetermines the uniqueness of properties. What is the structure of dendrimers? These systems are regular and well organized. Growth of a particle originates from a functional central point and proceeds by building up layer by layer, each layer consisting of monomers branching like a tree. It is important to strictly control the completeness of each previous layer (”generation”) to correctly construct the next one, because, as it was established, functional characteristics of the molecule strongly depend on number of layers. For instance, melt viscosity abruptly increases by 8-10 orders due to transition from fifth to sixth dendrimer generation, whereas viscosity of classical polymers grows exponentially. During first 10 years, we had even to prove that the dendrimers have a polymeric nature, albeit differently organized. Next to the dendrimers, there were less regular, but easier accessible hyperbranched polymers, multiarm stars, nanogels, etc. We had to reveal and understand specifics of each of these objects.
As a result, we have built a model for the whole class of such objects, which explains where they behave as macromolecules and where as nanoparticles. It was shown that a hyperbranched macromolecule can transform into a colloidal particle due to intramolecular cyclization and then begins to behave as a particle with all characteristic features inherent in this state of matter; namely, it interacts with environment only by means of its surface. In fact, these studies lead us to revision of the theoretical basis. We are claiming now that we have discovered a new type of links, which is realized in the dendrimers, and our goal at the theoretical level is to understand the nature of these links.
INEOS generates new knowledge, which is necessary to share with colleagues. How do you organize this process?
Indeed, we are really obliged to translate our vision of fundamental and applied problems of organoelement chemistry into other areas. At present, virtually the only possibility to communicate with the community consists in holding our scientific conferences. We traditionally hold at least four scientific meetings per year on the base of our Institute. For example, in 2015, we held Korshak’s lectures on chemistry of heat-resistant polymers and XIII All-Russian Andrianov’s conference “Organosilicon compounds: Synthesis, Properties, Application”. Fundamentally significant for us was also the V All-Russian conference with international participation for young scientists “Macromolecular nanoobjects and polymer nanocomposites”. It was devoted to comprehensive discussion and interpretation of qualitative transition of the polymer molecules to the polymer particles.
In 2016, we have five such events planned. We have scheduled the XI All-Russian Conference “Fluorine Chemistry” devoted to the 110th anniversary of one of founders of this science, academician I. L. Knunyants to be held in summer and the 11th International Symposium “Polycondensation-2016” to be held in autumn. Almost simultaneously with the Symposium, the seventh conference “Euroboron” (7th European Conference on Boron Chemistry) will take place. The very possibility to become organizers of such conference confirms international recognition of INEOS and high prestige of our scientists worldwide. This allows us to invite regularly the world’s leading experts, in given case, specialists in boron chemistry.
In order to attract attention of Russian young scientists to research themes of INEOS and integrate efforts around most urgent problems of organoelement chemistry, we called the First All-Russian conference on chemistry of organoelement compounds and polymers “INEOS OPEN 2015” last year. It was organized by us as a natural extension of the internal, domestic competitions for the best research work, which took place annually during as long as 60 years. To commemorate this anniversary, we decided to make it public and open to all professionals. We ensured the honest judging by forming a jury, in which invited experts constituted more than half of members. We invited leading scientists for the non-competitive plenary lectures as a kind of daily tuning fork to adjust level of presentations. Finally, we found sponsors. As a result, the competition passed with enchanting success. Now we see a sense to repeat it in 2016.
Will you continue to deal with applied or customized research activities while constantly talking about strategic orientation on fundamental studies?
Certainly. Applied research activities are necessary for us. We conduct many customized, contract studies, primarily in the field of polymers, fluorinated systems, and catalysts. However, none of these studies can replace basic researches; they organically combine with them. Applied investigations are conducted in those areas where we are in touch with the specific needs of customers.
Furthermore, we are currently negotiating with a number of companies producing and selling reagents. INEOS has implemented technologies allowing producing many substances that may be in demand in the Russian market of chemicals. Taking into consideration current exchange rate, such domestic production of unique reagents may be quite profitable. To start, we need to choose the most promising positions, analyze existing groundwork, and establish collaboration with business structures. This is a very difficult job, for which the Institute creates a special unit.
We are ready to cooperate with the industry in terms of import substitution. Analytical opportunities of INEOS that are based on one of the best laboratories of microanalysis as well as few up-to-date spectroscopic laboratories are very high. These laboratories allow analyzing samples of various materials at the highest possible level. Moreover, we are ready and even prefer to offer a customer more advanced analogues rather than simply obtain and interpret results of samples analysis.
In general, we are ready to work with any customers who address us with their specific problems. INEOS is completely open for collaboration.
Thank you for the interesting story.
Interview with A.M.Muzafarov was
prepared by K.Gordeev and I.Shakhnovich
Institute of Organoelement Compounds of RAS named after A.N.Nesmeyanov (INEOS) had been targeted at fundamental studies in one of the most promising and dynamically developing branches of organoelement chemistry ever since its foundation in 1954. However, scientists never restricted their research efforts by pure theory; they implemented obtained results in mass production processes and products in demand at variety of markets, from medicine, textile fabrics, and food to fine chemicals and defense-related components.
Emerging 21st century had initiated the next, fourth, scientific and technical revolution, including new materials with unique properties, amazing production processes, and, as a consequence, the need in a principal reconstruction of many industries. Chemistry of organoelement compounds is among those scientific and technical sciences, which largely determine progress in up-to date industrial technologies. How do scientists of INEOS respond to these challenges? This was told to us by Aziz Mansurovich Muzafarov, the famous specialist in the field of organosilicon compounds, director of INEOS, and full member of RAS.
Aziz Mansurovich, INEOS is one of the world and Russia leading academic research centers in the field of organoelement chemistry. What are the most important problems facing the Institute at present?
INEOS is really one of world’s leading research centers in the field of basic research organoelement chemistry. Its specifics and main research areas were defined by the founder of INEOS, President of the USSR Academy of Sciences, Alexander Nikolayevich Nesmeyanov. It is commonly believed at present that science is interdisciplinary, that discoveries are made at the junction of sciences. Meanwhile, academician Nesmeyanov said about these junctions as points of accelerated scientific and technological growth as far back as 60 years ago. Moreover, properly speaking, he founded our Institute just as cross-disciplinary project at the interface of organic and inorganic chemistry, where rapid development had been expected.
In fact, INEOS was the first institution of this kind. Although it was intended primarily for public researches, the Institute had allowed a number of “closed” academicians to conduct basic studies and win a worldwide recognition. In this view, the Institute had been equipped with the latest state-of-the-art facilities including a very reasonably arranged scientific instrument park, workshop, pilot sets, and the conference hall, which even now allows to hold international conferences.
A lot has happened since those days. The Institute has a quite incredible service record and history. It is enough to say that INEOS was the very same place where the beautiful polyhedral structures such as carboranes and metallasiloxane compounds were discovered. Commonly known products that had become the pride of Soviet chemistry of those times such as an artificial red and black caviar, popular synthetic textile fiber Lavsan (the word “lavsan” is derivative from the name of our laboratory for macromolecular compounds, in Russian “Laboratoriya Vysokomolekulyarnykh Soyedineniy”, which had developed this material), etc. had been created here. The list of similar innovations that were later used in wide range of industries is very long. Nevertheless, in spite of those successes, INEOS never planned to transform into an applied institution. We always were and we are aimed at the development of fundamental concepts in chemistry of main classes of organoelement compounds such as organometallic, organoboron, organosilicon, organophosphorus, and organofluoric compounds.
The valuable experience gained by the Institute over the past years has allowed creating a number of new scientific schools that uniquely combined organic, organoelement, coordination, and physical chemistry as well as the chemistry of macromolecular compounds and natural biologically active substances. However, some blurring of initial research directions took place as a result. Demand for organoelement compounds has risen sharply in many industries, and at some point, our research increasingly become concentrated in the adjacent application areas. While the Institute had started in 1954 with a dozen of laboratories, their number rose up to 54 by 2010. However, today basic researches in the field of organoelement chemistry are imperative of our era.
We had discussed the situation at one of sessions of INEOS Scientific Council and concluded that we needed to concentrate efforts and go back to fundamental principles, that is, to advancement in initial research directions. We decided that only 25 laboratories plus 10 interim research groups are enough for this purpose. The concept of interim research groups is adopted as basic structural principle in virtually all scientific institutes (at least institutes of RAS Division of Chemistry). It permits to avoid disintegration of research units and multiplication of research directions inside the units. At the same time, emerging specific promising ideas are studied by research groups that are formed only on a temporary basis. Researchers in a group have three years to prove or reject the proposed idea. Of course, nobody requires a discovery from such group since a scientific knowledge is the matter of high priority here and either positive or negative result are of equal importance. However, if an idea was proved true, and the group managed to develop it during that time, then this group can apply for foundation of new laboratory. Otherwise, nothing bad happens, the scientists will return to their previous working positions in order for preparing to next attempt. Such organizational approach allows Institute, on the one hand, to follow the main research directions associated with main classes of organoelement compounds, and, on the other hand, to conduct pioneer researches in the frontier areas.
Of course, such reorganization hardly can solve all problems. In particular, one acute issue of today is the revival of several lost directions that had been successfully developed in INEOS in the past and are obviously in demand both today and in the future. Unfortunately, we have lost a number of scientific schools. A typical example is formerly very strong laboratory of organoaluminum compounds, which are the components, in particular, of the very important catalytic systems and propellants. Another example is researches of polyphosphazenes belonging to one of the unique types of polymers, which were synthesized in INEOS at the highest unique level. However, in the past years of economic reconstruction, normal funding was discontinued while demand for some innovations was virtually ceased. Consequently, progress has stopped, and survival began. Many researchers left the Institute, some died, others changed specialty. In absence of leaders, these directions stopped development.
Very large efforts and investments are required now to restore appropriate levels in these fields. It is necessary, however, to do this, because the main purpose of INEOS, as we see it today, is to rise up to a new level of research, thus make a breakthrough, and create a scientific basis for new generations of technologies. This task requires concentration of research efforts on the fundamental issues of chemistry of organoelement compounds, i.e. on problems that were the initial purpose of INEOS.
I would like to underline once more that this is imperative of our era. If we want to stay members of the highly developed countries club, we need to rebuild the Russian industry in jump-like manner as dictated by the breakthrough strategy. However, technological breakthrough rarely arises due to inspiration only; it should be performed on a strong fundamental basis. Therefore, the deeper we will be able to work out a certain direction, the more probable a breakthrough will be.
What technological breakthroughs in the field of organoelement compounds do you expect?
Let us look at the direction closest to me – silicones. Today, processes of third generation are commonly used for their preparation. The first generation, from which all it began, was based on the reaction of tetrachlorosilane conversion into esters of orthosilicic acid. Then the time of the organomagnesium synthesis based on Grignard reagents had come. Main types of silicone products were produced using just second-generation processes. Then there was another technological revolution caused by the discovery of the chlorosilane direct synthesis method enabled to obtain the basic silicone monomer, dimethyldichlorosilane, directly from silicon and methyl chloride in a single step reaction. The silicones market had responded immediately since the companies that largely invested into organomagnesium synthesis turned out to be losers. Economics of production based on old or new processes had been proved quite different. To use new processes, it was necessary to purchase licenses from patent holders.
It should be noted here that silicones represent the area of industrial production owned by only highly developed countries. In fact, it was club of five World Powers. The Soviet Union was a member of this club absolutely legitimately, because in 40-50-s it built its own industry of these substances production based on the third-generation technologies. We produced the entire wide range of silicone products, from rubber and varnishes to adhesives and glues. From the methodological point of view, it was a completely original development of Soviet chemical engineers. Nobody sold us patents in those times.
The new industry has been created by efforts of team of scientists headed by academician Kuzma Andrianovich Andrianov, one of the founding fathers of organosilicon chemistry as a whole. I would like to emphasize that the complete system was created, designed to meet the demand for silicones primarily in the aviation and space engineering. The scientific support was provided by a number of specialized laboratories, including the laboratory for organosilicon compounds of our institute. Qualified specialists for the industry had been trained by the faculty headed by academician K. A. Andrianov at Moscow Institute of Fine Chemical Technology named after M. V. Lomonosov. Finally, of course, the bedrock of the industry was the creation of the branch technological institute GNIIChTEOS (State Research Institute for Chemistry and Technology of Organoelement Compounds) owing to great efforts made by K. A. Andrianov. GNIIChTEOS was a kind of technological center, in which experts from various academic and industrial institutions were collected. No processes could be implemented at production plants without debugging and trials in GNIIChTEOS. The production plants had been constructed simultaneously. There were five such production plants, each being specialized in specific products.
Thus, a strong scientific and industrial foundation, from basic research to technological development and production, was put into base of the Soviet silicone full-cycle production. Moreover, it was a well-managed centralized system. This system broke down when the coordinating body, USSR State Committee on Science and Technology, which linked the production practice with academic developments, disappeared. In a certain sense, academic institutions in that time found themselves in vacuum while productive enterprises stopped production because they were strongly centralized and they did not know how to work in the market. For this reason, industrial production of silicones in former USSR, which reached about 100 thousand tons in 1991, was substituted for import of silicones, which reached almost the same amount, 90 thousand tons, in 2010. It means that silicones market has remained, but it is now not ours. That is why there is no sense just to restore and reproduce what was done before.
Our industry seems to be lucky compared with others: it succeeded to preserve, although partly, manufacturing capabilities and preclude ruination of GNIIChTEOS (now this institute is attached to the holding “RT-Chemcomposite” being part of the Rostec State Corporation). Now closed-cycle production of silicone monomers is restored at the Kazan factory of synthetic rubber for the first time in many years. This enterprise will operate using old, well-known processes, but it is evident now that its capacity is not enough to control entire market. Nevertheless, the good news is that this enterprise will allow keeping technological culture and ability to design and implement innovations as well as to solve some problems of import substitution and import independence in defense industries.
However, in order to regain a leading position in the production of silicones, Russia needs a transition from the existing technologies of their production to the new, fourth-generation, processes, which will create a real advantage over potential competitors. I say ‘potential’ because we are not real competitors yet.
What principles will be put into base of the fourth generation of silicone production technology? Why do you think that the domestic industry has the ability to implement them before the others?
The fourth generation will be based on chemical reactions that do not use chlorine. At present, the process flowchart for producing these substances (third generation) is arranged as follows. First, chlorosilanes are synthesized. Then they are converted into the siloxane intermediates and products for further processing using processes of hydrolytic polycondensation. We have opened novel catalytic processes based on alkoxysilanes rather than chlorosilanes, which allow rebuilding the entire silicone chemistry by excluding any chlorine derivatives from it. Now alkoxysilanes can be obtained directly from alcohols and silicon in one-step. This provides benefits in almost all stages of the silicones production flowchart. Besides, production of alkoxysilanes by direct synthesis ensures a number of additional advantages rather than being simply more effective. First, chlorosilanes are not far away from chemical warfare agents and hence require great care in handling unlike alkoxysilanes, which can be produced in virtually any environment.
Large companies leverage chlorosilanes in their manufacturing cycles since just chlorosilanes make it easier to command at the market. After all, very large investments are required to launch such production including recycling technologies. Of course, today processes of third generation are advanced up to perfection, so that columns of direct synthesis somewhere in Wales may well be installed as closely as 300 meters from a school, owing to ideal process control and strictly guaranteed safety. Nevertheless, chlorine is chlorine, and if you make use of chlorinated derivatives to produce monomers, then you must recycle them afterwards.
However, it looks quite different when you switch to alkoxysilanes: only very lazy may say that it is too hard for him to recycle these substances. Therefore, it is not simply switching to a next process generation, but qualitatively very different perception of the silicone production process. In fact, it is a very different economy, in which silicones cease to be very specific, difficult to manufacture products.
Here many opportunities open just for domestic enterprises. Firstly, the whole world is now working on the technological groundwork of 20–30 years old. Naturally, the companies engaged in the production of silicones closely monitor all innovations around the world. Nevertheless, even if a technological breakthrough took place there, nobody will immediately begin to close operating plants and switch to a new technology, at least as long as he or she will compensate all previous investments. This circumstance gives us a time handicap of 3–5 years, of course, if we are able to quickly create new technologies. It is why research in this direction is one of our priorities. We are ready to production of certain alkoxysilane types, but a lot of work is still to be fulfilled to implement all required product line.
In general, silicone products have one huge advantage – they are fully recyclable. We can fully rework them into initial materials, that is, decompose a piece of silicone rubber onto components (monomers and filler) and then turn them again into the same rubber. Such deep reworking in combination with the chlorine-free process make silicones unique and promising products.
Moreover, we can already speak about the fifth generation of processes, when it will be possible to produce silicones directly from silicon oxide – silica (simply stated, quartz sand) rather than pure silicon by attaching organics directly to it. In other words, we can eliminate one more stage, recovery of silicon from the sand, out of the production process. Such attempts have already been made, but so far, they are still those swallows that do not make spring. Nevertheless, they determine a strategic research vector.
In general, we clearly understand what you need to do in the field of silicone chemistry. Of course, many interesting things can be done within paradigm of the third generation as well, but there hardly will be a breakthrough. Nevertheless, the breakthrough is imperative, as it was explained above.
In which directions is it supposed to develop chemistry and technology of other main classes of organoelement compounds?
Each of these classes of substances is very specific, and hence strategies of research development are very different from each other. In some cases, we are already seeing the following process stage, while in other cases, only progressive accumulation of knowledge and technological evolution are observable. However, in all cases we can point out the problems that need to be addressed first.
For example, situation in the area of organophosphorus compounds is very similar to the area of organosilicon compounds: in both areas, there is the problem of transition to chlorine-free productive methods. Organophosphorus chemists at present have advanced in the process technology much further than their colleagues, organosilicon chemists. At the same time, organophosphorus chemists have a very acute problem with the industrial implementation. The country has lost a great share of both technological groundwork and organophosphorus compounds production facilities. There is no even an institute similar to GNIIChTEOS, which could be responsible for implementation of new methods in manufacturing technology. At present, the only available option seems to be in collaboration with very powerful corporations that produce phosphate fertilizers. We must try to convince them of the need to diversify their business.
In general, progress in the fields of organoboron and organofluoric chemistry has the form of gradual evolution. Preparative methods and productive processes for both classes of compounds are well studied and advanced, although the problem of synthesis simplification and conditions optimization always stays urgent. On the other hand, range of applications for both classes of substances is very wide; the demand for them is high, whereas unique properties allow looking for new application areas.
In particular, main trend in chemistry of organoboron compounds in INEOS consists in preparation of carboranes, which first were synthesized by us simultaneously with the Americans in the early 1960s. Carboranes are molecules with a specific structure built of carbon, boron, and hydrogen atoms. They have appearance of spatially cyclic macromolecules (macrocycles) very similar to fullerenes and possess many interesting features. A propos, fullerenes were first calculated by theorists of our institute as well; authors named them “footballens” because of their resemblance to a soccer-ball. Carboranes find many various applications from fuels additives and components of adhesives to drugs used in neutron capture therapy of cancer. Carborane-based liquids have very unusual rheological properties that are promising for future use.
In contrast, chemistry of organofluorine compounds is the chemistry of hydrophobic and superhydrophobic substances. All neutral super oil-resistant coatings and rubbers are based on organofluorines. “Blue Blood” (artificial blood substitute based on perfluorocarbons) is also organofluorines, which are remarkable also for huge oxygen solubility. Experiments are known, in which a mouse fully immersed in the perfluorocarbon liquid could quietly “breathe”during a very long time.
Another important area is preparation of new fluorinated hydrophobisators with reactive silicon-containing functional groups. Such substances easily bind to any surface and therefore are attractive for application as highly adhesive coatings. The researches aimed at organofluorines application in supercritical media have a no less strong potential. They play a great role in detoxification of soils with excessive herbicides content. A special INEOS-initiated program of the Russian Foundation for Basic Research focused on this research area was even started in 2015.
The primary task facing the Institute in the field of organofluorine compounds consists in transition from experimentation to industry, from retort to productive processes. Fortunately, here we have someone to rely on. Our partner in technological development in fact grown out of our Institute is the Research & Production Association “P & M-Invest”, which produces organofluoric reagents.
Once more INEOS general direction from “Nesmeyanov’s bunch” is related to chemistry of organometallic compounds. Such compounds are in demand by a variety of industries including the defense ones, where, in particular, they are used as fuel combustion regulators. Certain prospects are connected also with application of organometallic compounds in catalytic reactions.
Organometallic compounds are actively used to produce drugs in the fine organic synthesis, too. Moreover, certain organometallic compounds are drugs themselves. A striking example is the iron-containing compound ferrocene, which was studied intensively still during the life of academician A. N. Nesmeyanov. The pharmaceutical composition ferroceron was developed based on this substance.
Among promising research directions I would like to note lanthanide-based organometallic compounds. These rare earth elements are not so rare and expensive, as many think; they are sincerely practicable.
Generally speaking, almost all basic researches that are “praise rather than pudding”, are valuable precisely in that they lead to a true understanding of what and how is happening in chemical systems and in fact are themselves the door to the future. Often researches yield nothing of what originally expected, but sometimes the unexpected result determines the future development direction.
Can you provide some example of such unexpected, opening new horizons, research result?
Yes, of course. There is one amazing class of substances among polysiloxanes, which have a very eloquent name “dendrimers”, in other words, polymers with a tree-like, fractal structure. At the same time, these molecules have nearly circular shape. It is hard to propose a higher technology in chemistry. The compounds are very interesting in relation to both structure and properties. In this view, they can be considered as either macromolecules or almost spherical particles. Due to this unique combination of properties, dendrimers are now increasingly used in biological studies, medicine, catalytic and photochemical processes. The number of promising application areas is permanently growing.
Indeed, as A. M. Butlerov taught, the uniqueness of structure predetermines the uniqueness of properties. What is the structure of dendrimers? These systems are regular and well organized. Growth of a particle originates from a functional central point and proceeds by building up layer by layer, each layer consisting of monomers branching like a tree. It is important to strictly control the completeness of each previous layer (”generation”) to correctly construct the next one, because, as it was established, functional characteristics of the molecule strongly depend on number of layers. For instance, melt viscosity abruptly increases by 8-10 orders due to transition from fifth to sixth dendrimer generation, whereas viscosity of classical polymers grows exponentially. During first 10 years, we had even to prove that the dendrimers have a polymeric nature, albeit differently organized. Next to the dendrimers, there were less regular, but easier accessible hyperbranched polymers, multiarm stars, nanogels, etc. We had to reveal and understand specifics of each of these objects.
As a result, we have built a model for the whole class of such objects, which explains where they behave as macromolecules and where as nanoparticles. It was shown that a hyperbranched macromolecule can transform into a colloidal particle due to intramolecular cyclization and then begins to behave as a particle with all characteristic features inherent in this state of matter; namely, it interacts with environment only by means of its surface. In fact, these studies lead us to revision of the theoretical basis. We are claiming now that we have discovered a new type of links, which is realized in the dendrimers, and our goal at the theoretical level is to understand the nature of these links.
INEOS generates new knowledge, which is necessary to share with colleagues. How do you organize this process?
Indeed, we are really obliged to translate our vision of fundamental and applied problems of organoelement chemistry into other areas. At present, virtually the only possibility to communicate with the community consists in holding our scientific conferences. We traditionally hold at least four scientific meetings per year on the base of our Institute. For example, in 2015, we held Korshak’s lectures on chemistry of heat-resistant polymers and XIII All-Russian Andrianov’s conference “Organosilicon compounds: Synthesis, Properties, Application”. Fundamentally significant for us was also the V All-Russian conference with international participation for young scientists “Macromolecular nanoobjects and polymer nanocomposites”. It was devoted to comprehensive discussion and interpretation of qualitative transition of the polymer molecules to the polymer particles.
In 2016, we have five such events planned. We have scheduled the XI All-Russian Conference “Fluorine Chemistry” devoted to the 110th anniversary of one of founders of this science, academician I. L. Knunyants to be held in summer and the 11th International Symposium “Polycondensation-2016” to be held in autumn. Almost simultaneously with the Symposium, the seventh conference “Euroboron” (7th European Conference on Boron Chemistry) will take place. The very possibility to become organizers of such conference confirms international recognition of INEOS and high prestige of our scientists worldwide. This allows us to invite regularly the world’s leading experts, in given case, specialists in boron chemistry.
In order to attract attention of Russian young scientists to research themes of INEOS and integrate efforts around most urgent problems of organoelement chemistry, we called the First All-Russian conference on chemistry of organoelement compounds and polymers “INEOS OPEN 2015” last year. It was organized by us as a natural extension of the internal, domestic competitions for the best research work, which took place annually during as long as 60 years. To commemorate this anniversary, we decided to make it public and open to all professionals. We ensured the honest judging by forming a jury, in which invited experts constituted more than half of members. We invited leading scientists for the non-competitive plenary lectures as a kind of daily tuning fork to adjust level of presentations. Finally, we found sponsors. As a result, the competition passed with enchanting success. Now we see a sense to repeat it in 2016.
Will you continue to deal with applied or customized research activities while constantly talking about strategic orientation on fundamental studies?
Certainly. Applied research activities are necessary for us. We conduct many customized, contract studies, primarily in the field of polymers, fluorinated systems, and catalysts. However, none of these studies can replace basic researches; they organically combine with them. Applied investigations are conducted in those areas where we are in touch with the specific needs of customers.
Furthermore, we are currently negotiating with a number of companies producing and selling reagents. INEOS has implemented technologies allowing producing many substances that may be in demand in the Russian market of chemicals. Taking into consideration current exchange rate, such domestic production of unique reagents may be quite profitable. To start, we need to choose the most promising positions, analyze existing groundwork, and establish collaboration with business structures. This is a very difficult job, for which the Institute creates a special unit.
We are ready to cooperate with the industry in terms of import substitution. Analytical opportunities of INEOS that are based on one of the best laboratories of microanalysis as well as few up-to-date spectroscopic laboratories are very high. These laboratories allow analyzing samples of various materials at the highest possible level. Moreover, we are ready and even prefer to offer a customer more advanced analogues rather than simply obtain and interpret results of samples analysis.
In general, we are ready to work with any customers who address us with their specific problems. INEOS is completely open for collaboration.
Thank you for the interesting story.
Interview with A.M.Muzafarov was
prepared by K.Gordeev and I.Shakhnovich
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