Olefin Polymerization Catalysts
Development of a New Generation of Olefin Polymerization Catalysts Using the Combinatorial Approach and High-Throughput Techniques
Tech Area / Field
- CHE-POL/Polymer Chemistry/Chemistry
- CHE-SYN/Basic and Synthetic Chemistry/Chemistry
3 Approved without Funding
Moscow State University / Department of Chemistry, Russia, Moscow
- Scientific Research Institute of Chemistry and Technology of Organo-Element Compounds, Russia, Moscow
- Basell Polyolefins GmbH, Germany, Ludwigshafen\nLos-Alamos National Laboratory / Chemistry Division, USA, NM, Los-Alamos\nUniversität Konstanz, Germany, Konstanz
Project summaryUntil recently in catalyst research high-throughput methods of research have not been applied. The first report on such approaches appeared 4-5 years ago. SYMYX in currently regarded as an absolute leader on the US market. This company has developed a high-throughput laboratory system for olefin polymerization catalyst screening, and supplied it to Dow Chemical (USA), ExxonMobil (USA), and Sumitomo (Japan). Such laboratories are built over a 2x48 polymerization reactors manifolds. A full testing cycle can be done within 4 hours, which allows to perform up to 96 tests per shift. Though the SYMYX laboratory, which includes all testing and analytical instrumentation required for the characterization of polymers and control of polymerization, costs over 10 M$, it is worth these money, as its application allows to considerably shorten the development of a given catalyst from 10-12 years normally required using the conventional methods, to 2-2.5 years. The other combinatorial catalysis companies in the US are Argonaut Technologies and Torial. In Europe the leaders in combinatorial catalysis are Avantum Technologies (the Netherlands) and HTE (Germany).
Two issues should be considered during the realization of high throughput system for polymerization catalyst development. First, the sources of potential catalysts should be manifold: besides screening available samples and conventional synthesis, a high output procedures for parallel concurrent synthesis of 10s and 100s of new compounds employing fast and highly reliable transformations of organometallic compounds (OMC). The same should be applicable to co-catalysts and promoters. The companies working in the catalyst screening business are known to develop the techniques of concurrent synthesis. The extension of this approach to new families of catalysts is highly desirable. Secondly, the procedures used for the polymerization catalyst testing as well as the study of structure and physico-chemical parameters of polymers need further refinement.
Moreover, there is one more important incentive for the development of catalyst screening. Indeed, currently major industrial processes are gas-phase polymerization of ethene and propene, suspension polymerization of ethene, and propene polymerization in liquid monomer solution. In all of these processes highly effective catalysts (e.g. Ziegler-type catalysts) are used. Technological and economical reasons command the application of heterogeneous (supported) catalysts (SPS), which, however, suffer from considerable inhomogeneity of active centers distribution and modest net activity. Supported catalysts of new generation are expected to overcome these essential drawbacks. New generation supported metallocene catalysts feature active centers of rigorously defined structure to be uniformly distributed over the surface. Such catalyst, based both on metallocenes and transition metal chelates, shall allow to design polymerization set-ups with fully automated control. On the other hand, any quantitative theoretical reasoning for supported catalysts a much more sophisticated procedure than that for homogeneous catalysts, well beyond current level of theoretical calculations. Thus, empirical high-throughput screening is apparently the only way to new generation catalysts and processes.
Thus, the aim of this project is to develop new combinatorial methods, particularly in the paralleized synthesis of potential catalyst libraries, as well as their testing as polymerization catalysts, both homogeneous and supported. Though the project involves several tasks generally ascribed to fundamental research (such as the development of new catalyst families as well as parallel synthesis and testing methodology), as a whole it belongs to applied science, as soon as the following practically feasible goals are involved:
1. The development of parallel synthesis of various classes of organometallic compounds both as homogeneous and supported applicable as advanced polymerization catalysts, which should further be employed by the leading chemical and petrochemical companies for manufacturing purposes.
2. The development of methods of high-throughput testing of olefin polymerization catalysts, and in selected cases, of high-throughput testing of the resulting polymers. The methods developed are supposed to find application in R&D studies of the leading chemical companies.
3. As a result of research mentioned in the preceding clauses a new class of olefin polymerization catalysts should be developed. For the best representatives of this class the work shall be advanced to the development of technologically feasible methods of synthesis. Further, after the thorough testing and marketing studies, a single process shall be selected for the elaboration of full-scale technology, including the pilot set-up for optimization of the process at the industrial scale. The resulting technology shall be transferred to the chemical industry for full-scale implementation.
During the works at stage 1 the applicants shall synthesize new classes of organometallic compounds and supported systems to test these compounds in olefin polymerization. The analysis of results thus obtained shall enable the selection of the most interesting catalysts for further elaboration. The means of optimization, as well as the most effective approaches shall be elucidated. For the implementation of combinatorial approach we shall have to determine the parental structures which can give rise to the libraries of organometallic compounds (OMC) with similar structures. Thus, the main goal of stage 2 is the development of preparative methods leading to the selected parental structures, and their structural investigations with the use of all available instrumental methods. The goal of stage 3 is the selection of the best performing, in what concerns the catalytic activity and selectivity, homogeneous and supported catalytic systems (SPS) with the aid of the combinatorial chemistry and high-performance parallel synthesis. This research aims at the study of methods of modification of parental OMC for the synthesis of libraries of homogeneous olefin polymerization catalysts, the synthesis of new libraries of homogeneous and supported olefin polymerization catalysts from the parental organometallic compounds using both conventional methods and high-throughput parallel synthesis methods, and testing of these catalyst libraries in olefin polymerization using both the conventional and advanced parallel testing equipment. Main goals of stage 4 is the development of technology of parallel synthesis of homogeneous and supported catalysts, as well as technologies of parallel testing of olefin polymerization catalysts, and methods of parallel studies of structure and properties of product polyolefins. The top performers among the homogeneous and supported olefin polymerization catalysts tested at stage 3 shall be selected. In order to elucidate the possibilities to use these catalysts at industrial scale, technologically feasible method of synthesis should be developed at stage 5. Though the development of technology of synthesis and polymerization are outside of the scope of this project, the preliminary analysis of possible methods of synthesis shall be performed with the aim to suggest the methods allowing for scaling up in the industrial equipment.
The applicants possess a long-term experience in organometallic chemistry, homogeneous catalysis (including olefin polymerization), synthesis and studies of supported catalysts, structural studies of organic and organometallic compounds, as well as metal complexes immobilized on solid support with the aid of the whole range of advanced physico-chemical methods. The project team includes the researchers from Chemistry Department of Moscow State University and Federal State Unitary Enterprise “State Research Institute of Chemistry and Technology of Organoelement Compounds.”
As soon as the majority of the applicants has been earlier engaged in the development of mass-destruction weapons, the project fits nicely one of the main declared goals of ISTC, that is to provide the possibility to such scientists to move to the civilian research. As such area of research the project offers the development of a new methodology for the search for advanced technologically feasible olefin polymerization catalysts.
Apart from apparent implications for the fundamental theory of catalysis, the project aims at the solution of practical challenges, which are discussed in detail above. From the economical viewpoint the project aims at dramatic shortening of the development cycle for an inpidual catalyst from 10-12 years required today to 2-2.5 years. Thus the solution of tasks of the project should lead to achieve an essential increase of research labor effectiveness during the development of new catalysts, as well as to develop new branches of advanced polymers and materials. These goals are thus in accord with the national interests of Russian Federation, and other countries which contribute to ISTC foundation.
The project also implies an intensive cooperation between the Russian, German, and US scientists, as an essential involvement of foreign collaborators is planned at several stages of work. A real-time exchange of samples and research data between the applicants and collaborators is planned. The collaborators are supposed to lend the assistance in the selection of the most interesting homogeneous and supported olefin polymerization catalysts, as well as in the development of technology of parallel testing of the catalysts, and particularly in the studies of structure and properties of polymers obtained. Such materials are to be subject of joint patenting, which is likely to be essentially facilitated due to the help from the collaborating parties. The collaborators are supposed to apply the methods and technologies in their laboratories, thus serving to ensure the reproducibility and coherence of the results obtained by the applicants. If necessary, the collaborators may lend their unique instrumentation for sample testing and elaboration of the techniques under development.
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