Preparation of styrenated oil by controlled/living radical polymerization in miniemulsion

In the first part of the thesis, styrenated oil products were prepared in miniemulsion conditions by reversible addition-fragmentation chain transfer polymerization (RAFT) technique using phenacyl morpholine dithiocarbamate (PMDC) as a RAFT agent. First, hydroperoxide groups were formed on the oil structure by air-blowing process. Then the prepared miniemulsion of styrene-air blown linseed oil (ABLO) was subjected to styrenation in the presence of the RAFT agent. Miniemulsion was prepared by means of ultrasonication by using cetyl trimethyl ammonium bromide (CTAB) and hexadecane (HD) as surfactant and co-surfactant, respectively. Ideal miniemulsion condition was determined by following the change of droplet/particle sizes during the reactions carried out at different surfactant concentrations. The styrenated oil product obtained under optimum conditions was characterized by FT-IR, 1H-NMR and GPC measurements. In order to understand the effect of miniemulsion conditions on molecular weight and polydispersity index (PDI), styrenated oil samples were also prepared in solvent (dioxane) medium for the purpose of comparison. Tests for film properties of product prepared by RAFT in miniemulsion medium were applied according to related standards. The styrenated oil obtained in this way exhibit molecular weight distribution values (1.71 and 1.76 for 24 h and 48 h, respectively) which are lower than styrenated oil products obtained by the classical RAFT polymerization in solvent medium. The film properties showed that these styrenated oil samples could be used as an oil based binder. In the second part of the thesis, triglyceride oil-styrene copolymerization was carried out with nitroxide mediated radical polymerization (NMRP) technique in miniemulsion. 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 glicerydes (PGs) of linseed oil 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 PDI and good film properties in miniemulsion medium. Miniemulsion mixture was prepared by ultrasonication process by using DOWFAX 8390 and HD as surfactant and costabilizer, respectively. Miniemulsion polymerization was carried out at different surfactant concentrations in order to determine the appropriate surfactant concentration. Droplet and particle sizes were followed throughout the reaction in each process. 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 to understand the effect of miniemulsion medium. Film properties of oil samples were evaluated according to related standards. As a result, styrenation process could be successfully carried out with NMRP adapted miniemulsion polymerization preserving colloidal stability and samples obtained in this process showed low PDI values and good film properties.