from first principles PP-I-1

PP-II-8The Mechanism of the Controlled Radical Polymerization of Acrylic Estersby Using of New Iniferters on the Basis of ThiocompoundsFarzaliev R. 1 , Nasirov F. 1,2 , Markova E. 1 , Erbay E. 2 , Janibayov N. 11 Institute of Petrochemical Processes of National Academy of Sciences of Azerbaijan, Baku,Azerbaijan2 Petkim Petrokimya Holding, Izmir, Turkeyfnasirov@petkim.com.trIn traditional radical polymerizations recombination and disproportionation reactions of radicalsare carried out very quickly and, therefore the active centers practically aren’t protected from thereactions of bimolecular termination. At enough higher monomer conversions, synthesizedpolymers are characterized with the broad molecular-weight distributions (M w /M n ~3, andsometimes even more than 5) that have significant negative influences on some their properties.In a controlled/”living” radical polymerization the irreversible bimolecular chain termination isreplaced by the reversible reaction of chain growing radicals with the fragments of the initiatorand/or special additives - iniferters, introduced into the polymerizate in the “catalytic” amounts. Alabile end group, capable in certain terms to disintegrate with the regeneration of initial or newactive radical which continues growth of a polymeric chain, appears as a result of chaintermination. The process of repeated termination and growth (“sleep” and “life”) of the polymerchain provides a stepwise increase in the material chains during polymerization.The purpose of this research is to investigate the mechanism of controlled/”living” radicalpolymerization reaction of alkyl-acrylate monomers (in particular, butyl-acrylate and2-ethylhexyl-acrylate) in presence of different radical initiators (benzoyl peroxide, izopropilbenzolehydroperoxide, di-cumyl-peroxide, etc) and new iniferters on the basis of organicO,O-di-alkylaryl-dithiophosphates, S-alkyl-aryl-thiophosphates, in particular.In the chain of growing radical-regulators- iniferters, synthesized by us, the possibility of initiationof polymerization practically absents, which conduces to the synthesis with high yields(90-95%) oligomers and polymers of alkyl-akrylates with very narrow molecular-massdistributions. We set the optimum terms of synthesis of poly-alkyl-akrylates (in particular, polybutyl-acrylateand poly-2-ethylhexyl-acrylate) with narrow molecular-mass distribution (withinthe limits of 1,05-1,5), which can be used as viscosity additive for the base motor oils. As thecontrolled radical polymerization and ordinary free radical polymerization occurs with theparticipation of radical particles, these processes are characterized by a number of common linesand features, and applicable for polymerization practically of the same range of monomers. At thesame time there are some considerable distinctions between them and we’ll be report about it inthis presentation.139