• Several PEO-b-P2VP diblock and triblock copolymers have been synthesized by anionic polymerization;
• PHEGMA-b-PDEAEMA and PEO-b-PDEAEMA diblock copolymers have been synthesized by group transfer polymerization and ATRP, respectively;
• Studies of micelle formation and characterization have been performed my pH-metry. Dynamic light scattering, AFM;
• A new method for synthesis of diblock and triblock PEO-b-P4VP copolymers by ATRP has been developed; both diblock and triblock copolymers were synthesized; conditions of gel formation for triblock copolymer have been determined;
• Bimetallic colloids Pd/Au, Pd/Pt, and Pd/Zn were synthesized in PS-b-P4VP micelles and characterized; dependence of catalytic properties in DHL hydrogenation on bimetallic structure was studied; ultrasonic activation of Pd monometallic heterogeneous catalyst resulted in 1.6-fold increase of activity;
• Pd and Pt colloids were synthesized in PEO-b-P2(4)VP, PEO-b-DEAEMA, and POEGMA-b-DEAEMA micelles in aqueous medium at various pH and in PE layers deposited on alumina and characterized by elemental analysis, AFM, XRD, and TEM;
• Catalytic activity and selectivity of homogeneous and heterogeneous catalysts derived from the systems mentioned above were studied in selective DHL hydrogenation; the best catalytic system was found to be PEO-b-P2VP-Pd (99.0% selectivity at 100% conversion); mathematical modeling of the kinetics of homogeneous and heterogeneous hydrogenation with the catalysts was carried out; ultrasonic treatment of PEO-b-P2VP-Pd/Al2O3 allowed increasing its selectivity in DHL hydrogenation;
• Measurements of surface tension of hydrogenation reaction mixture components and contact angles between these components and solid substrate (SiO2) have been carried out;
• Conditions for PE deposition on Al2O3 were optimized; three colloidal catalysts prepared by deposition of PE (layer-by-layer) on alumina support followed by metallation have been developed;
• Catalytic activity and selectivity of five samples of Pt catalysts (two PEO-b-P2VP-Pt/Al2O3 and three PDADMAC-Pt-Al2O3) have been studied in L-sorbose direct oxidation to 2-KGA; the best results so far (99% selectivity at 87% conversion) were found for the catalyst derived from block copolymer synthesized by Greek group;
• A new computer simulation methodology has been developed for the analysis of light scattering in strongly scattering media

• Optimization of synthesis of PEO-b-P4(2)VP, PEO-b-DEAEMA, and PHEGMA-b-DEAEMA diblock and triblock copolymers of different composition;
• Continued investigation of the micellar behavior of diblock and triblock copolymers;
• Theoretical investigation of micelle formation in block copolymer aqueous solutions;
• Synthesis and characterization of Pd and Pt colloids formed in block copolymer micelles in different conditions and in PE-based systems; AFM and TEM examination; ASAXS data processing;
• Study of catalytic properties of Pd- and Pt-containing catalysts based on block copolymers (diblock and triblock copolymers and PE) in DHL hydrogenation and L-sorbose oxidation; study of the reaction kinetics; ultrasonic activation of the catalysts;
• Physicochemical investigation of the reactions mixture components (XP- and IR-spectroscopy);
• Optimization of DHL hydrogenation and L-sorbose oxidation in pilot reactors; accumulation of the products.

Implementation of Results
Pilot reactor of 0.16 m³ capacity has been prepared for testing experiments on direct L-sorbose oxidation to 2-KGA in Shop 04 at OAO “Belgorodvitaminy”. Batch method for oxidation has been chosen, which allows achieving 99% selectivity. The settings providing necessary oxygen flow rate, mixing and temperature (65-70 °C) have been constructed and tested idling. For DHL hydrogenation, first tests have been also conducted in a pilot reactor of 0.16 m3 capacity with fixed-bed layer of the catalyst. Novel technology of L-sorbose oxidation has attracted two more end-users to the Project results: ICN “Marbiopharm” (Yoshkar-Ola, Russia) and AC “Sintvita” (Tulsky region, Russia).

NATO Consultant:  Professor Adi Eisenberg, McGill University, Canada
 
Abbreviations:
AG – acetylene glycol; ATRP - atom transfer radical polymerization; DHL - dehydrolinalool (3,7-dimethyl-octaene-6-yne-1-ol-3); EG – ethylene glycol; INEOS - Nesmeyanov Institute of Organoelement Compounds; 2-KGA – 2-keto-L-gulonic acid; LN – linalool; PE - polyelectrolyte; PEO-b-P2(4)VP - poly(ethylene oxide)-block-poly-2(4)-vinylpyridine; PEO-b-DEAEMA - poly(ethylene oxide)-block-poly(2-(diethylamino)ethylmethacrylate); PHEGMA-b-DEAEMA - poly(hexa(ethylene glycol) methacrylate)-block-poly(2-(diethylamino)ethylmethacrylate),  PS-b-P4VP - polystyrene-block- poly-4-vinylpyridine