Colloidal particles with magnetic properties have become increasingly important both technologically and for fundamental studies. Here, chemical initiator-free miniemulsion polymerization of styrene and butyl acrylate has been performed for preparation of magnetic nanocomposite particles with the diameter of 81-150 nm in the presence of sodium dodecyl sulfate as surfactant, span 80 as stabilizer, and hexadecane as hydrophobe. The polymerization reaction was initiated and progressed under ultrasonic irradiation, generated by immersed probe into the latex. The key point in achievement of encapsulation of modified Fe 3 O 4 nanoparticles was preparation of a stable colloidal dispersion at the end of the reaction. The obtained products in each step were characterized by FTIR spectroscopy. Dynamic light scattering analysis was used to follow particle size diameter of the samples. Morphology of the particles and formation of core-shell structure were analyzed by SEM and TEM micrographs, respectively. TGA and magnetometry of the polymeric films confirmed the extent of insertion of used magnetite and their corresponding behavior.
Three types of polystyrenes were prepared at different temperatures of 50, 150 and 250°C by bulk thermal polymerization of styrene below 20 percent of conversion. The assignment of all stereosequences at pentad level of quaternary aromatic carbon and hexad level of methylene carbon of the polystyrenes were done using 13C Liquid NMR in deuterated chloroform at similar conditions. Bernoullian and first-order Markov statistics were calculated and the results were compared with experimental NMR results. It is shown that first-order Markov statistics fit slightly better than Bernoullian statistics for the assigned carbons. The results indicated that by increasing polymerization temperature the probability of meso addition (Pm) in polystyrene chains was enhanced. Pm was calculated for polystyrenes prepared at 50, 150 and 250°C and corresponding values were 0.378, 0.398 and 0.402 respectively. It was shown that by increasing temperature the polymerization is directed toward the Bernoullian propagation. By increasing the NMR acquisition temperature from 20 to 65°C higher resolution especially in quaternary aromatic carbon was achieved and the related peak was splitted to 16 peaks corresponding to a heptad level compared to 10 peaks in 20°C.
Low molecular wieght 1,2-polybutadiene (Aldrich) tacticity was determined by 13CNMR (100.6 MHz). It was found that the olefinic methylene carbon has the highest splitting and a combination of pentad and heptad sequences was determined which is in agreement with the theoretical calculations. For the first time aliphatic methine carbon assignment of 1,2-polybutadiene was performed. Furthermore, olefinic methine carbon assignment was also performed and the results were compared with the theoretical calculations. For all carbons Bernoullian and first-order Markov-chain propagation statistics were used to fit the experimental data and a good agreement was obtained indicating an atactic polymer (Pm= 0.467). It was shown that the most probable reaction before gelation which happens by heating the polymer under vacuum at 250°C, is crosslinking accompanied with methyl group formation. The decrease in double bond intensity of the pendant group together with constant cis and trans double bond intensities were observed. During heating the syndiotactic triad sequences are consumed indicating that no cyclization has happened.
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