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Iron-containing imidazolium-based ionic liquids were successfully applied as catalysts in the styrene polymerization. Solventless conditions, organic solvents and different imidazolium-based ionic liquid catalysts were tested to evaluate the best reaction conditions. The ionic liquids BMI.FeCl 4 and BMI.Fe 2 Cl 7 showed very distinct catalytic activities. Schulz–Flory distributions indicate two or three active catalytic species in different distributions. Via on-line direct infusion electrospray (tandem) mass spectrometry (ESI-MS(/MS)) reaction monitoring, both active catalytic species in accordance with the Schulz–Flory distributions were intercepted and characterized, providing important mechanistic insights that allowed us to propose a rationale for the origin of the superior catalytic efficiency. [ABSTRACT FROM AUTHOR]

In this work, the emulsion copolymerization of styrene and acrylated methyl oleate (AMO), a monomer derived from oleic acid (OA), has been evaluated. Reactions exhibiting high monomers conversions were successfully performed, leading to the formation of very stable polymer lattices, whose average particle size is kept unchanged for relatively high storage times. The average molar masses determined by gel permeation chromatography showed to be very dependent on the amount of AMO in the reaction medium, presenting experimental values within the range from 280 000 to 39 000 g mol−1 with molar mass dispersity ranging from 4 to 2 when the AMO fraction in the reaction medium was increased to 40 wt%. The nucleation rate was affected by AMO in such way that an increase in AMO concentration must be accompanied by an increase in initiator concentration, which leads to the reduction of the average molar masses of the copolymer. The thermal analyses of the polymer materials showed that the glass transition temperature decreased with increasing amount of AMO in the copolymer chains. Practical applications: The use of vegetable oils and their derivatives as precursor monomers in polymerization reactions has increased each day due to their renewable origin. Among them, OA deserves special attention due to the high availability and ease of chemical modification, mainly when the double bounds are considered. Results showed that AMO could be incorporated at high ratios in emulsion polymerization reducing the glass transition temperatures of the copolymer. The polymer lattices also showed good storage stability. [ABSTRACT FROM AUTHOR]

This work presents a mathematical model for semibatch carboxylated styrene/butadiene (XSBR) emulsion polymerizations, intended for the online and real-time data reconciliation and monitoring of the polymerization reactor. Proposed procedures assume that some parameters must be estimated in real time, for accommodation of the unavoidable fluctuations of industrial operation conditions. Pressure, temperature, and feed rate profiles are used for parameter estimation, allowing for real-time prediction of important properties of XSBR latexes, including monomer conversions, solids contents, and copolymer compositions. The proposed scheme was validated with actual data obtained in Pilot-plant and full-scale reactors. In all cases, estimated n values ranged from 0.1 to 1.7, which agree with results reported previously. As observed at plant, heat transfer coefficients can change from batch-to-batch and experience large changes during the batch due to modification of the reactor volume and accumulation of polymer material on the heat transfer areas. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers [ABSTRACT FROM AUTHOR]

The ionic liquid 1‐n‐butyl‐3‐methylimidazolium heptachlorodiferrate (BMI.Fe2Cl7) is efficiently used as catalyst in the cationic emulsion polymerization of styrene. The effect of different reaction temperatures, surfactant, and ionic liquid concentrations on polymer properties as molecular weight distribution and particle size is evaluated. High weight average molecular weights, above 1000 kDa, are achieved at 70% of conversion in 100 nm polystyrene particles formed mainly by micellar nucleation. Particle sizes and molecular weights increase with the decrease of the amount of surfactant. Even at low concentrations, BMI.Fe2Cl7/styrene molar ratio equal to 1/1000, the ionic liquid proves to be efficient for the emulsion polymerization of styrene, and lower ionic liquid concentrations lead to the formation of longer polymer chains. [ABSTRACT FROM AUTHOR]

This work reports the use of acrylated fatty acid methyl ester (AFAME) as a biomonomer for the synthesis of bio‐based hybrid magnetic particles poly(styrene‐co‐AFAME)/γ‐Fe2O3 produced by miniemulsion polymerization. Poly(styrene‐co‐AFAME)/γ‐Fe2O3 can be tailored for use in various fields by varying the content of AFAME. The strategy employed is to encapsulate superparamagnetic iron oxide nanoparticles (SPIONs) as γ‐Fe2O3 into a styrene/AFAME‐based copolymer matrix. Raman spectroscopy is employed to ensure the formation of the SPIONs (γ‐Fe2O3) obtained by a co‐precipitation technique followed by oxidation of Fe3O4. The functionalization of SPIONs with oleic acid (OA) is carried out to increase the SPIONs–monomer affinity. The presence of OA on the surface of γ‐Fe2O3 is certified by identification of main absorption bands by fourier‐transform infrared spectroscopy (FTIR). Thermal analysis (differential thermogravimetry/differential thermo analysis and differential scanning calorimetry) results of poly(styrene‐co‐AFAME)/γ‐Fe2O3 show an increase in AFAME content leading to a lower copolymer glass transition temperature (Tg). Dynamic light scattering (DLS) measurements result in poly(styrene‐co‐AFAME)/γ‐Fe2O3 particles with diameter in the range of 100–150 nm. It is also observed by transmission electron microscopy (TEM) and cryo‐TEM techniques that γ‐Fe2O3 particles are successfully encapsulated into the poly(styrene‐co‐AFAME) matrix. The biomonomer obtained from soybean oil (AFAME) is used for the synthesis of bio‐based hybrid magnetic particles, poly(styrene‐co‐AFAME)/γ‐Fe2O3, by miniemulsion polymerization. As a principal strategy, the superparamagnetic iron oxide nanoparticles γ‐Fe2O3 are encapsulated into styrene/acrylated fatty acid methyl ester (AFAME)‐based copolymer matrix. The properties of poly(styrene‐co‐AFAME)/γ‐Fe2O3 can be modulated depending on its use by varying the amount of AFAME. [ABSTRACT FROM AUTHOR]

For the first time, it was shown the cationic miniemulsion polymerization of styrene using an ionic liquid as catalyst. The ionic liquid (BMI·Fe 2 Cl 7 ) was tolerant to the presence of high amount of water, being effective for polymerization of styrene in the evaluated temperatures range from 70 to 90 °C. The polymerization was considerably slower than conventional cationic polymerization, indicating that this process is easier to control than the conventional ones. In addition, quite high molecular weights were reached, while the particle size, between 150 and 175 nm, was within the typical range for miniemulsion polymerization. [ABSTRACT FROM AUTHOR]