A. M. Aladyshev

Synthesis of propylene-ethylene copolymers in liquid propylene using ansa-metallocenes of the C 1 symmetry

The copolymerization of ethylene with propylene in the liquid propylene initiated by ansa-metallocenes of the C 1 symmetry, rac-[1-(9-η5-fluorenyl)-2-(5,6-cyclopenta-2-methyl-1-η5-indenyl)ethane]zirconium dichloride and rac-[1-(9-η5-fluorenyl)-2-(5,6-cyclopenta-2-methyl-1-η5-indenyl)ethane]hafnium dichloride, activated by methylaluminoxane has been studied. Triisobutylaluminum has been used as a cocatalyst. The propylene-ethylene copolymers thus prepared contain 5–60 mol % ethylene units. The reactivity ratios have been measured. In the case of the zirconocene-based catalyst, the molecular mass of the copolymers decreases with an increase in the content of ethylene units. The reverse situation is observed in the case of the hafnocene-based catalytic system. The copolymers are characterized by the low T g values (down to −45°C). Incorporation of a small amount of ethylene units (5 mol %) results in a rise in the elastomeric behavior of the polymers.

Homo-and copolymerization of vinylcyclohexane with α-olefins in the presence of heterogeneous and homogeneous catalytic systems

The polymerization and copolymerization of vinylcyclohexane with α-olefins in the presence of several heterogeneous and homogeneous catalytic systems were studied. It was shown that, with respect to activity in the polymerization of vinylcyclohexane, the tested catalysts can be arranged in the following order: α-TiCl3 < titanium-magnesium catalyst < metallocene catalyst. Poly(vinylcyclohexane) prepared with heterogeneous catalytic systems is a solid semicrystalline polymer. The properties of polymers synthesized with homogeneous systems differ substantially depending on the type of the metallocene used. In the presence of metallocenes with a C2 symmetry, crystalline powderlike products arise, while in the case of metallocenes with C1 and C s symmetries, polymerization yields amorphous viscous products. Molecular-mass distributions of poly(vinylcyclohexane) samples prepared using both heterogeneous titanium-magnesium catalysts and homogeneous metallocene complexes show a bimodal pattern, indicating the heterogeneity of active centers of these catalysts. Upon introduction of a comonomer (ethylene, propylene, and 1-hexene) into the reaction mixture, the activity of all studied catalytic systems increases. When Me2C(3-Me-Cp)(Flu)ZrCl2 and rac-Me2SiInd2ZrCl2 are used as catalysts, the degree of crystallinity of the copolymers grows owing to the presence of ethylene or propylene units in poly(vinylcyclohexane) chains.

Synthesis of isotactic copolymers of 4-methyl-1-pentene by living polymerization catalyzed by zirconium non-metallocene complexes

Amorphous isotactic poly(4-methyl-1-pentene) was synthesized from 4-methyl-1-pentene in the presence of the zirconium complex (η5-C5Me5)ZrMe[PhCH2NC(Me)N-tert-Bu][B(C6H5)4] as a catalyst of living polymerization and characterized. A number of linear isotactic copolymers of 4-methyl-1-pentene with 1-hexene and functionalized olefins, such as 5-(trialkylsiloxy)-1-pentene, were prepared under similar conditions. The feasibility of chemical modification of the functionalized copolymers to yield hydroxylated copolymers was studied. All the polymers obtained were characterized by means of the GPC, DSC, X-ray diffraction, and 13C and 1H NMR techniques.

Bulk propylene polymerization in the presence of ansa-metallocenes of C2 and C1 symmetries: From a rigid thermoplastic to elastomeric stereoblock polypropylene

Bulk propylene polymerization in the presence of ansa-metallocenes with C2 and C1 symmetries has been studied. The catalytic activity, polymerization kinetics, and the molecular weight of polypropylene (PP) depend strongly on catalyst formation conditions. Mixtures of rac and meso isomers of metallocenes make it possible to rapidly produce a high-molecular-weight isotactic PP with high stereoregularity and mechanical characteristics and thus skip the stage of the isolation of pure rac isomer in the catalyst synthesis. The ability of triisobutylaluminum to serve as a cocatalyst is studied for ansa-metallocenes of C1 symmetry. In this case, the molecular weight of PP is higher, indicating that organoaluminum compounds participate in chain termination reactions. An increase in the reaction temperature results in an increase in the stereoregularity and crystallinity of PP. Polypropylene synthesized using ansa-metallocenes of C1 symmetry has good elastomeric properties.

Isospecific Bulk Polymerization of Propylene with the Use of ansa-Metallocenes as a Mixture of rac and meso Isomers

The effects of various pathways of the formation of catalytic systems based on the rac-Me2SiInd2ZrCl2 metallocene on the activity and properties of polypropylene prepared by the bulk polymerization of propylene were studied in detail. It was found that the conditions of formation of the catalytic system affect not only its activity and the character of kinetic curves but also the molecular weight of the synthesized polymer. Propylene polymerization was studied with the use of a number of bisindenyl derivatives of zirconium, which were mixtures of rac and meso forms that differ in the nature of substituents in the Si bridge or the indenyl ligand. The conclusion was drawn that, with the use of metallocenes as a mixture of rac and meso forms, high-molecular-weight isotactic polypropylene can be prepared with high stereoregularity at a very high rate; thereby, the stage of separation of a pure rac isomer can be excluded in the synthesis of the catalyst.

Biodegradation of Poly-ε-caprolactones and Poly-l-lactides by Fungi

This work assessed biodegradation, by Aspergillus, Fusarium, Penicillium and Parengyodontium fungi, of four samples of poly-ε-caprolactone (PCL), three samples of poly-l-lactide (PLA) and one sample of poly-d,l-lactide (DL-PLA) produced by ring-opening polymerization initiated by aluminium complexes of corresponding lactones. Mesophilic fungal strains actively biodegrading PCL (F. solani) and PLA (Parengyodontium album and A. calidoustus) were selected. The rate of degradation by the selected fungi was found to depend on the physicochemical and mechanical properties of the polymers (molecular weight, polydispersity, crystallinity). The most degradable poly-ε-caprolactone sample was shown to have the lowest molecular weight; the most biodegradable polylactide DL-PLA had the lowest crystallinity. Mass spectral analysis of biodegraded polymer residues showed PCL to be degraded more intensively than PLA. It is established that in the case of Parengyodontium album the colonization of the films of polypropylene composites with DL-PLA is observed, which will undoubtedly contribute to their further destruction under the influence of abiotic factors in the environment.

The Particularities of Isospecific Polypropylene Synthesis in Bulk with Ansa-metallocene Catalysts

hiral ansa-metallocenes with indenyl ligands are useful as catalysts for producig isotactic polypropylene (iso-PP). In this work the kinetics of propylene polymerization in bulk with ansa-zirconocenes C2 symmetry at 30-80’C with using of different cocatalysts, mainly the polymethylaluminoxane, have been investigated. The following aspects were in focus of our interest: the nature of the bridge, the presence of substituents in the bridge and on the indenyl ligands; conditions of the pre-activation stage and the polymerization process and the study of relations between these parameters and PP properties. Using the Me2Si(4-Ph-2-Et- Indenyl)2ZrCl2 (rac : meso = 1 : 2)/MAO the high molecular iso-PP was produced. The activity during iso-PP synthesis reaches 900 kgPP/gcat.h. Influence of hydrogen on activity and molecular weight characteristics also were studied. We compared properties of metallocene iso-PP with the same of PP produced with heterogeneous catalytic Systems on the base of high effective Ti/Mg catalysts.