Abstract: In this study, triglyceride oil-styrene copolymerization was carried out with nitroxide mediated radical polymerization (NMRP) technique in miniemulsion medium. For this purpose, firstly, 4,4-azobis-4-cyanopentanoyl chloride (ACPC) was synthesized from 4,4-azobis-4-cyanopentanoic acid (ACPA). Macroazoinitiator which comprises thermally labile azo groups was obtained with reaction of partial glycerides (PGs) and ACPC. Then, oil-based macroazoinitiator and styrene mixture was subjected to styrenation in the presence of nitroxide radical 2,2,6,6-tetramethylpiperidinyl-1-oxy (TEMPO) in order to obtain styrenated oil product with low polydispersity index (PDI) in miniemulsion medium. Miniemulsion mixture was prepared by ultrasonication process by using DOWFAX 8390 and hexadecane (HD) as surfactant and costabilizer, respectively. Miniemulsion polymerization was carried out at different surfactant concentrations in order to determine the ideal surfactant concentration. For this purpose, droplet/particle sizes were measured throughout the reaction and the surfactant amount for the least change in droplet/particle size was determined. Products obtained by ideal process were characterized by FT-IR, 1H-NMR and GPC measurements. Styrenation process was also performed by solution polymerization in xylene for the purpose of comparison with the miniemulsion medium. It was understood that, styrenation process carried out successfully with NMRP adapted miniemulsion polymerization because colloidal stability could be achieved.Film properties of styrenated oil samples were determined to related standards. The obtained styrenated oil samples showed good film properties and could be used as a coating material.

Keywords: Miniemulsion, NMRP, linseed oil, binder, styrenated oil.