Metallocene Catalytic Insertion Polymerization of 1-Silene to Polycarbosilanes.
ABSTRACT: Metallocene of zirconium were used as a catalyst for an insertion polymerization of 1-methylsilene directly into pre-ceramic precursor polyzirconocenecarbosilane (PZCS) during dechlorination of dichlorodimethylesilane by sodium, which exhibits high catalytic effectiveness with the maximum conversion ratio of polycarbosilane up to 91%. The average molecular weights of polymers synthesized are less than 1400, all with very narrow polymolecularities. The mechanism of catalytic polymerization was assumed to be similar to a coordination insertion polymerization of 1-olefins by metallocenes. The obtained PZCS show high ceramic yields with formation of composite ceramics of ZrC-SiC, which are novel polymeric precursors of ultra-high temperature ceramic (UHTC) fiber and composite.
Project description:In single-site olefin polymerization catalysis, a large excess of cocatalyst is often required for the generation of highly active catalysts, but the reason for this is unclear. In this work, fundamental insight into the multifaceted role of cocatalyst methylaluminoxane (MAO) in the activation, deactivation, and stabilization of group 4 metallocenes in the immobilized single-site olefin polymerization catalyst was gained. Employing probe molecule FT-IR spectroscopy, it was found that weak Lewis acid sites, inherent to the silica-supported MAO cocatalyst, are the main responsible species for the genesis of active metallocenes for olefin polymerization. These weak Lewis acid sites are the origin of AlMe2+ groups. Deactivation of metallocenes is caused by the presence of silanol groups on the silica support. Interaction of the catalyst precursor with these silanol groups leads to the irreversible formation of inactive metallocenes. Importantly, a high concentration of MAO (14 wt% Al) on the silica support is necessary to keep the metallocenes immobilized, hence preventing metallocene leaching and consequent reactor fouling. Increasing the loading of the MAO cocatalyst leads to larger amounts of AlMe2+, fewer silanol groups, and less metallocene leaching, which all result in higher olefin polymerization activity.
Project description:Recent reports have shown that ferrocene displays an unexpected combination of force-free stability and mechanochemical activity, as it acts as the preferred site of chain scission along the backbone of highly extended polymer chains. This observation raises the tantalizing question as to whether similar mechanochemical activity might be present in other metallocenes, and, if so, what features of metallocenes dictate their relative ability to act as mechanophores. In this work, we elucidate polymerization methodologies towards main-chain ruthenocene-based polymers and explore the mechanochemistry of ruthenocene. We find that ruthenocene, in analogy to ferrocene, acts as a highly selective site of main chain scission despite the fact that it is even more inert. A comparison of ruthenocene and ferrocene reactivity provides insights as to the possible origins of metallocene mechanochemistry, including the relative importance of structural and thermodynamic parameters such as bond length and bond dissociation energy. These results suggest that metallocenes might be privileged mechanophores through which highly inert coordination complexes can be made dynamic in a stimuli-responsive fashion, offering potential opportunities in dynamic metallo-supramolecular materials and in mechanochemical routes to reactive intermediates that are otherwise difficult to obtain.
Project description:Bis(1-methylethenyl-cyclopentadienyl)zirconium dichloride (7a) was prepared by a fulvene route. Photolysis at 0 degrees C with Pyrex-filtered UV light resulted in a rapid and complete intramolecular [2+2]cycloaddition reaction to yield the corresponding cyclobutylene-bridged ansa-zirconocene dichloride isomer (8a). This is one of the rare examples of an organic functional group chemistry that leads to carbon-carbon coupling at the framework of an intact sensitive group 4 bent metallocene complex. More sterically hindered open metallocenes that bear bulky isopropyl or tert-butyl substituents at their Cp rings in addition to the active 1-methylethenyl functional group undergo the photochemical ansa-metallocene ring closure reaction equally facile. The metallocene systems used and obtained in this study have served as transition metal components for the generation of active metallocene propene polymerization catalysts.
Project description:One of the most efficient and versatile ways to synthesize polyolefin nanocomposites is the in-situ polymerization of olefins in the presence of nano particles by metallocene catalysts. Metallocene/methylaluminoxane (MAO) catalysts are soluble in hydrocarbons and therefore they can be absorbed perfectly in solution onto the surface of particles or fibers and after addition of ethene or propene they can then catalyze a polyolefin film on the surface. Metallocene/MAO and other single site catalysts allow the synthesis of polymers with a precisely defined microstructure, tacticity, and stereoregularity as well as new copolymers with superior properties such as film clarity, high tensile strength and lower content of extractables. The polymer properties can be enlarged by the incorporation of nanofillers. The resulting polyethylene or polypropylene nanocomposites give a tremendous boost to the physical and chemical properties such as dramatically improved stiffness, high gas barrier properties, significant flame retardancy, and high crystallization rates.
Project description:Hafnium complexes have drawn attention for their application as post-metallocene catalysts with unique performance in olefin polymerization. In this work, a series of half-metallocene HfMe2 complexes, bearing a tetrahydroquinoline framework, as well as a series of [Namido,N,Caryl]HfMe2-type post-metallocene complexes, bearing a tetrahydrophenanthroline framework, were prepared; the structures of the prepared Hf complexes were unambiguously confirmed by X-ray crystallography. When the prepared complexes were reacted with anhydrous [(C18H37)2N(H)Me]+[B(C6F5)4]-, desired ion-pair complexes, in which (C18H37)2NMe coordinated to the Hf center, were cleanly afforded. The activated complexes generated from the half-metallocene complexes were inactive for the copolymerization of ethylene/propylene, while those generated from post-metallocene complexes were active. Complex bearing bulky isopropyl substituents (12) exhibited the highest activity. However, the activity was approximately half that of the prototype pyridylamido-Hf Dow catalyst. The comonomer incorporation capability was also inferior to that of the pyridylamido-Hf Dow catalyst. However, 12 performed well in the coordinative chain transfer polymerization performed in the presence of (octyl)2Zn, converting all the fed (octyl)2Zn to (polyolefinyl)2Zn with controlled lengths of the polyolefinyl chain.
Project description:50 years ago, Karl Ziegler and Giulio Natta were awarded the Nobel Prize for their discovery of the catalytic polymerization of ethylene and propylene using titanium compounds and aluminum-alkyls as co-catalysts. Polyolefins have grown to become one of the biggest of all produced polymers. New metallocene/methylaluminoxane (MAO) catalysts open the possibility to synthesize polymers with highly defined microstructure, tacticity, and steroregularity, as well as long-chain branched, or blocky copolymers with excellent properties. This improvement in polymerization is possible due to the single active sites available on the metallocene catalysts in contrast to their traditional counterparts. Moreover, these catalysts, half titanocenes/MAO, zirconocenes, and other single site catalysts can control various important parameters, such as co-monomer distribution, molecular weight, molecular weight distribution, molecular architecture, stereo-specificity, degree of linearity, and branching of the polymer. However, in most cases research in this area has reduced academia as olefin polymerization has seen significant advancements in the industries. Therefore, this paper aims to further motivate interest in polyolefin research in academia by highlighting promising and open areas for the future.
Project description:BACKGROUND: Monomeric Group IVB (Ti, Zr and Hf) metallocenes represent a new class of antitumor compounds. There is literature on the general biological activities of some organotin compounds. Unfortunately, there is little information with respect to the molecular level activity of these organotin compounds. We recently started focusing on the anti-cancer activity of organotin polymers that we had made for other purposes and as part of our platinum anti-cancer effort. METHODS: For this study, we synthesized a new series of metallocene-containing compounds coupling the metallocene unit with dienestrol, a synthetic, nonsteroidal estrogen. This is part of our effort to couple known moieties that offer antitumor activity with biologically active units hoping to increase the biological activity of the combination. The materials were confirmed to be polymeric using light scattering photometry and the structural repeat unit was verified employing matrix assisted laser desorption ionization mass spectrometry and infrared spectroscopy results. RESULTS: The polymers demonstrated the ability to suppress the growth of a series of tumor cell lines originating from breast, colon, prostrate, and lung cancers at concentrations generally lower than those required for inhibition of cell growth by the commonly used antitumor drug cisplatin. CONCLUSION: These drugs show great promise in vitro against a number of cancer cell lines and due to their polymeric nature will most likely be less toxic than currently used metal-containing drugs such as cisplatin. These drugs also offer several addition positive aspects. First, the reactants are commercially available so that additional synthetic steps are not needed. Second, synthesis of the polymer is rapid, occurring within about 15 seconds. Third, the interfacial synthetic system is already industrially employed in the synthesis of aromatic nylons and polycarbonates. Thus, the ability to synthesize large amounts of the drugs is straight forward.
Project description:Methylaluminoxane (MAO) is an activator for single-site olefin polymerization catalysts. Structural characterization of MAO, and in particular the influence of its heterogenization on a silica support, is pivotal for the understanding and optimization of this versatile co-catalyst. In this work, we demonstrate that by varying the MAO loading on a silica support, we can tune the single particle characteristics in terms of MAO distribution and consequent activity. At low MAO loading we reveal two possible intraparticle MAO distributions: a homogeneous and an Al-shell type distribution. With increasing MAO loading, the interparticle MAO distribution becomes more homogeneous. Acidity probing measurements on the single particle level explain how a different intraparticle MAO distribution results in a different activity in metallocene activation. Al-shell particles contain remaining silanol groups and a negligible amount of acid sites and are, therefore, considered inactive for metallocene activation. Only the solid activator particles with a homogeneous intraparticle MAO distribution contain a sufficient number of acid sites, capable of activating the deposited metallocenes.
Project description:This paper is focused on the basic properties of ceramic composite materials used as thermal barrier coatings in the aerospace industry like SiC, ZrC, ZrB2 etc., and summarizes some principal properties for thermal barrier coatings. Although the aerospace industry is mainly based on metallic materials, a more attractive approach is represented by ceramic materials that are often more resistant to corrosion, oxidation and wear having at the same time suitable thermal properties. It is known that the space environment presents extreme conditions that challenge aerospace scientists, but simultaneously, presents opportunities to produce materials that behave almost ideally in this environment. Used even today, metal-matrix composites (MMCs) have been developed since the beginning of the space era due to their high specific stiffness and low thermal expansion coefficient . These types of composites possess properties such as high-temperature resistance and high strength, and those potential benefits led to the use of MMCs for supreme space system requirements in the late 1980s. Electron beam physical vapor deposition (EB-PVD) is the technology that helps to obtain the composite materials that ultimately have optimal properties for the space environment, and ceramics that broadly meet the requirements for the space industry can be silicon carbide that has been developed as a standard material very quickly, possessing many advantages. One of the most promising ceramics for ultrahigh temperature applications could be zirconium carbide (ZrC) because of its remarkable properties and the competence to form unwilling oxide scales at high temperatures, but at the same time it is known that no material can have all the ideal properties . Another promising material in coating for components used for ultra-high temperature applications as thermal protection systems is zirconium diboride (ZrB2), due to its high melting point, high thermal conductivities, and relatively low density . Some composite ceramic materials like carbon-carbon fiber reinforced SiC, SiC-SiC, ZrC-SiC, ZrB2-SiC, etc., possessing low thermal conductivities have been used as thermal barrier coating (TBC) materials to increase turbine inlet temperatures since the 1960s. With increasing engine efficiency, they can reduce metal surface temperatures and prolong the lifetime of the hot sections of aero-engines and land-based turbines.
Project description:Polycarbosilane (PCS) was used for surface modification of magnesium hydroxide (MNH) to enhance the flame retardant effectiveness by forming cohesive binding between MgO particles with ceramic adhesive. Chemical interaction and ceramic reaction were revealed between PCS and MNH, which made for a compact, thermal stable and ceramic-like barrier during the combustion of polyethylene (PE). The flame retardancy of PE/MNH/PCS composites was greatly enhanced and a limiting oxygen index (LOI) of 35.0 was achieved at the PCS/MNH ratio of 4/26 in the composite with 30 wt.% PCS modified MNH. Such results were superior in terms of high LOI value at low global content of MNH. Thanks to the better shielding effect of the integrated and self-supporting ceramic char, the peak heat release rate (p-HRR) and the total heat release (THR) of PE/MNH/PCS composites with 50 wt.% PCS modified MNH were remarkably decreased by 36% and 25% in comparison with PE/MNH with 50 wt.% MNH, respectively. The ceramic reaction between PCS and MNH, the superior thermal stability due to crosslinked PCS and the good barrier function of cohesive ceramic layer play important roles in the effective flame retardant mechanism.