from first principles PP-I-1

PP-III-91Direct Synthesis of Heterogenized Nickel- or Cobalt-Containing CatalyticDithiosystems for Polymerization of ButadieneRafieva S.R., Hasanova G.N., Nasirov F.A., Janibayov N.F.Institute of Petrochemical Processes of Azerbaijan National Academy of Sciences,30, Khodjaly ave., AZ 1025, Baku, Azerbaijanjnazil@mail.ru; j.nazil@yahoo.comNickel- or cobalt-containing dithioderivatives in combination with aluminorganic compounds(catalytic dithiosystems) show very high catalytic activity and selectivity in butadienehomogeneous polymerization process.It is know that an ideal catalyst combines the advantages of both homogeneous andhomogeneous catalysis. With this purpose we carried out an unusual method ofheterogenization of homogeneous catalysts for butadiene polymerization. The nickel- orcobalt-containing dithioderivatives were directly synthesized on OH-group of support (suchas silicates or zeolites).We carried out the reaction of direct phosphorosulfuration with P 2 S 5 of OH-groups of zeolitesuch as HLaY or HY. For it zeolite gel was released from excess of water by heating150-200 C. Reaction of phosphorosulfuration in the medium of xylene solvent was out at80-120 C. Using received dithiophosphorus fragment on the support and correspondingchloride, nitrate or sulphate salts of Ni and Co their heterogenized compounds have beensynthesized. The received compounds were identified by phosphorus content, also with themethods of IR-spectroscopy, DTA and X-ray analysis.Catalytic activities of synthesized heterogeneous dithiocompounds of Ni and Co in combinationwith aluminum organic compounds have been tested in reaction of solution, gas phase or blockpolymerization of butadiene. It was show, that against the homogeneous analogue, heterogenizedcompounds of Ni and Co show very high catalytic activity and selectivity in relation to formationof high stereoregular 1,4-cis polybutadiene. It was established, that even in the presence of nickelcompound it is possible to synthesize the high-molecular polybutadiene with intrinsic viscosity[η] = 1,0-2,5 dl/g and 1,4-cis isomer content 93,0% and higher, against [η] = 0,1-0,55 dl/g and1,4-cis isomer content no more than 80% in homogeneous catalyst. In the presence of cobaltcontaining heterogenized catalysts is in range of 500,0-1500,0 kg PBD/g M. hour, against40.0-100.0 kg PBD/g M. hour in a homogeneous variant.These new heterogenized nickel or cobalt-containing catalysts can be used in the solution,bulk, slurry (suspension) and gas phase polymerization processes of dienes.249