from first principles PP-I-1

PP-III-78Kinetic Regularities of 1-Decene Polymerization on SupportedTitanium-Magnesium Nanocatalysts (TMNC) and Molecular WeightCharacteristics of Obtained PolymersNesmelov A.I., Kleiner V.I., Ivanuk A.V., Smetannikov O.V., Chinova M.S.A.V. Topchiev Institute of Petrochemical Synthesis RAS, Moscow, Russiasmetannikov@ips.ac.ruSynthesis of high molecular weight polydecene (PD) on TMNC developed at the TIPS RASwas studied [1]. It is shown that the process takes place under mild conditions (20-60°C andatmospheric pressure) in aliphatic solvent. In order to establish the possibility of regulation ofthe catalyst stereospecific ability and activity and molecular weight of PD TMNC was usedboth itself, and being modified with internal (9,9-bis(methoxymethylen)fluorine) and/orexternal (cyclohexylmethyldimetoxysilane) electron donor (ED).It was found that the most active catalyst is unmodified (or basic) TMNC. The introduction ofexternal ED reduces the system resulting activity in 3.8 times (initial activity drops in14 times). Such a change in activity is typical in most cases of polymerization on titaniummagnesiumcatalysts modified with ED [2, 3]. Thus the ED does not change the monomersecond order up to the end of polymerization. The introduction of internal ED in anycombination with an external one or without it gives the first order. A notable violation of thefirst order is observed with increasing process temperature above 30°C. The activation energyof 1-decene polymerization is 91 kJ/mol e.g. very high and defines much lower rate of1-decene polymerization, compared with shorter α-olefins.TMNC is able to produce PD with molecular weight up to 4 mln and more, and with the EDintroduction the shift in molecular weight to higher values and the disappearance of thepolymer chains with a weight less than 700000 is observed. Similar effect is in a goodagreement with the theory of blocking with ED of active sites producing non-stereoregularlow molecular weight polymer chains.[1] Antipov E.M., Mushina E.A. et. al. Patent 2425059 Russia.[2] Zakirov M.I., Kleiner V.I. et. al. // Polym. Sci. Series B. 2010. V. 5. №9-10. P. 584.[3] Frolov I.M., Kleiner V.I. et. al. // Makromol. Chem. 1993. V. 194. №8. P. 2309.235