ABSTRACT
CpTiCl3/SiO2/MAO (Cp=cyclopentadienyl, MAO - methylaluminoxane) catalysts, where the Al:Ti varies from 20:1 to 500:1, were used in styrene polymerization. Atactic - syndiotactic polystyrene blends (aPS-sPS) were obtained in situ, the morphology of which was investigated by means of scanning electron microscopy. The blends morphology changed according to the kind of catalytic centers: cationic and syndiotactic on the catalyst surface, which create individually atactic or syndiotactic polystyrenes forming specific blends containing nano or micro-forms: when the Al:Ti ranges from 50:1 and to 100:1 in the blends, there occur nano-sPS particles 40-120 nm in size, if the Al:Ti≥300:1, the filament of δ-sPS polymorph, is produced where the filament size ranged from 30 to 10 nm. A decay of this form leads to the formation of spherical sPS forms several hundreds of nm in size. When the Al:Ti ranges 20:1-50:1, blend rods of several dozen micrometers were obtained.
ABSTRACT
Cyclopentadienyl-titanium complexes containing -OC6H4X ligands (X = Cl,CH3) activated with methylaluminoxane (MAO) were used in the homo-polymerization of ethylene, propylene, 1-butene, 1-pentene, 1-butene, and 1-hexene, and also in co-polymerization of ethylene with the alpha-olefins mentioned. The -X substituents exhibit different electron donor-acceptor properties, which is described by Hammett's factor (sigma). The chlorine atom is electron acceptor, while the methyl group is electron donor. These catalysts allow the preparation of polyethylene in a good yield. Propylene in the presence of the catalysts mentioned dimerizes and oligomerizes to trimers and tetramers at 25 degrees C under normal pressure. If the propylene pressure was increased to 7 atmospheres,CpTiCl2(OC6H4CH3)/MAO catalyst at 25 degrees gave mixtures with different contents of propylene dimers, trimers and tetramers. At 70 degrees C we obtained only propylene trimer. Using the catalysts with a -OC(6)H(4)Cl ligand we obtained atactic polymers with M(w) 182,000 g/mol (at 25 degrees C) and 100,000 g/mol (at 70 degrees C). The superior activity of the CpTiCl2(OC6H4Cl)/MAO catalyst used in polymerization of propylene prompted us to check its activity in polymerization of higher alpha-olefins (1-butene, 1-pentene, 1-hexene)and in co-polymerization of these olefins with ethylene. However, when homo-polymerization was carried out in the presence of this catalyst no polymers were obtained. Gas chromatography analysis revealed the presence of dimers. The activity of the CpTiCl2(OC6H4Cl)/MAO catalyst in the co-polymerization of ethylene with higher alpha-olefins is limited by the length of the co-monomer carbon chain. Hence, the highest catalyst activities were observed in co-polymerization of ethylene with propylene (here a lower pressure of the reagents and shorter reaction time were applied to obtain catalytic activity similar to that for other co-monomers). For other co-monomers the activity of the catalyst decreases as follows: propylene >1-butene > 1-pentene >> 1-hexene. In the case of co-polymerization of ethylene with propylene, besides an increase in catalytic activity, an increase in the average molecular weight M(w) of the polymer was observed. Other co- monomers used in this study caused a decrease of molecular weight. A significant increase in molecular weight distribution (M(w)/M(n)) evidences a great variety of polymer chains formed during the reaction.
Subject(s)
Alkenes/chemistry , Polymers/chemical synthesis , Titanium/chemistry , Catalysis , Ethylenes/chemistry , Molecular Weight , Organometallic Compounds/chemistryABSTRACT
The objective of this article is to inform readers of the European Community's programme of work on medical engineering research. An outline of the history of the European Community and its research programme is given. More specific information is then included on the current programme of work and, finally, an Appendix is given naming the national delegates to whom comments can be addressed and from whom further information can be obtained.
