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Magnetic materials based on iron oxides are extensively designed for several biomedical applications. Heterogeneous polymerization processes are powerful tools for the production of tailored micro-sized and nanosized magneto-polymeric particles. Although several polymerization processes have been adopted along the years, suspension, emulsion and miniemulsion systems deserve special attention due to its ability to produce spherical polymer particles containing magnetic nanoparticles homogeneously dispersed into the polymer thermoplastic matrices. The main objective of this paper is to review the main methods of synthesis of iron-based magnetic nanoparticles and to illustrate how typical polymerization processes in different dispersion medium can be successfully used to produce engineered magnetic core-shell structures. It is exemplified the use of suspension, emulsion and miniemulsion polymerization processes in order to support experimental methodologies required for the production of magnetic polymer particles intended for biomedical applications such as intravascular embolization treatments, drug delivery systems and hyperthermia treatment.

The current work was developed focusing on the synthesis of new polymeric latexes through the in reactor oxidative polymerisation of chia oil alkyd resins using the miniemulsion process. These latexes have potential applications, primarily in coating applications. Initially, an oil length mixture was obtained from chia oil through saponification and acidification reactions. The resulting mixture was characterized by 1H-NMR and 13C-NMR, confirming the presence of unsaturation and the characteristic functional groups associated with this compound. Phthalic anhydride and glycerol (esterification reaction) were used in the synthesis of alkyd resin. Alkyd resins were obtained by varying the oil length content in its composition: 30% wt% oil length alkyd resin is called short alkyd resin, 43% wt% oil length is medium resin and 64% wt% is the long alkyd resin. The 1H NMR spectra of alkyd resins showed peaks indicative of the presence of groups coming from phthalic anhydride and glycerol, as well as unsaturations that varied in intensity according to the size of the resin (short, medium or long). The miniemulsions were obtained from alkyd resins demonstrating colloidal stability over 90 days and with stable miniemulsions the oxidative polymerisation of the alkyd resins was carried out in a high-pressure reactor with temperature and pressure control and in the presence of the radicalinitiator benzoyl peroxide (BPO) and oxygen. Based on 1H-NMR analysis, polymers are formed through the oxidative polymerisation of alkyd resins from chia oil using the miniemulsion process. These polymers can be used as a paint base with a low solvent fraction or no solvent, depending on the application, and without using heavy metals-based catalysts. [ABSTRACT FROM AUTHOR]

The iron‐containing imidazolium‐based ionic liquids (ILs) 1‐n‐butyl‐3‐methylimidazolium heptachlorodiferrate (BMI.Fe2Cl7) and 1‐n‐butyl‐3‐methylimidazolium tetrachloroferrate (BMI.FeCl4) are applied as catalysts in the homogeneous polymerization of n‐butyl vinyl ether. Both solventless conditions as well as using different organic solvents, catalyst concentrations, temperatures, and reaction times are tested to assess the polymerization conditions that lead to the highest molecular weights of poly(n‐butyl vinyl ether). The Lewis acidic IL BMI.Fe2Cl7 proves to be highly efficient, even at low catalyst concentrations. In bulk polymerization, polymers with 142 kg mol−1 are obtained using a 1:10000 molar ratio of catalyst to monomer. In solution polymerization, the monomer consumption is also rapid and the molecular weight of the polymer is related to the catalyst concentration used. These results indicate the potential of this catalyst for industrial applications. In contrast with the acidic IL, the neutral iron‐containing imidazolium‐based IL BMI.FeCl4 does not show any catalytic activity. [ABSTRACT FROM AUTHOR]

Poly(vinyl pivalate) (PVPi) nanoparticles obtained via miniemulsion have particular properties useful for several applications. Thus, the present study aims to synthesize and characterize PVPi nanoparticles through the miniemulsion polymerization process, studying the effects of water‐soluble and oil‐soluble initiators, polymerization temperature, and the co‐stabilizer concentration on the final properties of the polymer, nanoparticle size, and conversion. The polymeric nanoparticles are characterized by Fourier transform infrared spectroscopy, nuclear magnetic resonance (1H and 13C NMR), thermogravimetric analysis, differential scanning calorimetry, gel permeation chromatography, dynamic light scattering, and transmission electron microscopy. The miniemulsion polymerization process ensures the formation of a polymeric fluid with high colloidal and thermal stability, with maximum conversions of ≈85% and average particle diameter of 97.2 ± 21.8 nm. The polymeric properties, such as molar mass and glass transition temperature (Tg), are influenced by process variables such as synthesis temperature and the type of initiator. The use of potassium persulfate and 2,2‐azobisisobutyronitrile (AIBN) initiators favors the homogeneous nucleation mechanism, resulting in a decrease in the average particle diameter and in the growth of the chains, result in greater average molar masses and, consequently, greater Tg. [ABSTRACT FROM AUTHOR]

Gas phase copolymerizations of ethylene and an α‐olefin comonomer are performed using a commercial Ziegler–Natta catalyst in the presence of different induced condensing agents (ICA). The impact of these factors on the yield and final polyethylene properties such as the melt flow index, crystallinity, and incorporation of comonomer is studied. It has been shown that the increase in the rate of polymerization is even more pronounced in the presence of ICA. It also appears that adding ICA to the copolymerizations changes the comonomer incorporation with respect to similar copolymerizations performed without ICA due to competing cosolubility effects. [ABSTRACT FROM AUTHOR]

Poly(vinyl pivalate) − PVPi is a poly(vinyl ester) that presents interesting characteristics that lead to the production of embolic agents, such as poly(vinyl alcohol) (PVA), with high level of sindiotacticity in contrast to the one synthesized from poly(vinyl acetate), for example. This work aims the study of the influence of process variables, such as stirring speed, amount of initiator, and suspending agent concentration on the suspension polymerization reaction of vinyl pivalate. Also, it has the objective of studying the way these parameters can influence the properties of the polymeric particles formation. For this purpose, the reaction system was evaluated using 550, 750, 950, and 1150 rpm as stirring speed, fraction of initiator in the range from 0.3 to 0.5 wt.%, and 0.5, 1.0, 1.5, 2.0, and 2.5 g L−1 of suspending agent. All samples were characterized by classical gravimetric measurements, proton nuclear magnetic resonance (1H‐NMR), gel permeation chromatography (GPC), and scanning electron microscopy (SEM). 1H‐NMR measurements confirmed the synthesis of poly(vinyl pivalate). SEM images have suggested the formation of particles with spherical morphology, exhibiting average diameters of 200, 122, 86, and 79 µm related to the stirring speed of 550, 750, 950 e 1150 rpm, respectively. It was also observed that the polymers had average molar mass of 6.7 · 105, 4.8 · 105, and 4.4 · 105 g mol−1 when 0.3, 0.4, and 0.5 wt.% of benzoyl peroxide (BPO) was employed, respectively. The global conversion achieved was ca. 90% in all conditions. [ABSTRACT FROM AUTHOR]

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]

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]

This work presents experimental results on the synthesis of soybean oil-based polymers through emulsion polymerization process. It was shown that polymeric materials can be successfully synthesized with high monomers conversion close to 100% and very high stability, displaying relatively high shelf-life time. Polymeric nanoparticles showing narrow particle size distribution, with average diameter around 80 nm (PdI = 0.213), determined via dynamic light scattering measurements were obtained. It was also observed by calorimetric analysis, that the final polymeric material presents two exothermic transitions and two glass transition temperatures. This complex thermal behavior probably takes place due to the nature of the monomeric mixture (AFFAM—acrylated linolenic, linoleic, and oleic acids in combination with methyl methacrylate), indicating that the final polymer presents a complex macromolecular arrangement. The glass transition temperature of the polymer lattices was reduced because of the AFFAM incorporation into the growing polymer chains, and additionally the thermal stability was improved. Regarding the average molar masses, it was observed that AFFAM comonomer plays an important role, leading to a decreasing in the mass-average molar mass when the AFFAM concentration is increased in the reaction medium. Depending on the AFFAM amount, the mass-average molar masses were found within the range from 70,000 g mol −1 to 890,000 g mol −1 with molar-mass dispersity lying in the interval from 1.7 to 2.4. [ABSTRACT FROM AUTHOR]

Enzymatically synthesised poly(glycerol adipate) (PGA) has shown a palette of key desirable properties required for a biomaterial to be considered a 'versatile polymeric tool' in the field of drug delivery. PGA and its variations can self-assemble into nanoparticles (NPs) and interact at different levels with small active molecules. PGA derivatives are usually obtained by functionalising the glyceryl side hydroxyl group present along the main polymer scaffold. However, if the synthetic pathways are not finely tuned, the self-assembling ability of these new polymeric modifications might be hampered by the poor amphiphilic balance. For this reason, we have designed a straightforward one-pot synthetic modification, using a small library of diols in combination with glycerol, aimed at altering the backbone of the polymer without affecting the hydrophilic glyceryl portion. The diols introduce additional functionality into the backbone of PGA alongside the secondary hydroxyl group already present. We have investigated how extra functionalities along the polymer backbone alter the final polymer reactivity as well the chemical and biological properties of the nanoparticles. In addition, with the intent to further improve the green credentials of the enzymatic synthesis, a solvent derived from renewable resources, (2-methyl tetrahydrofuran, 2-MeTHF) was employed for the synthesis of all the PGA-variants as a replacement for the more traditionally used and fossil-based tetrahydrofuran (THF). In vitro assays carried out to evaluate the potential of these novel materials for drug delivery applications demonstrated very low cytotoxicity characteristic against NIH 3T3 model cell line. [Display omitted] • Poly(glycerol adipate) (PGA) one-pot synthetic alteration using a series of diols. • Direct modification of the PGA backbone without affecting the glyceryl portion. • The diols used have introduced additional functionality into the backbone. • A renewably sourced solvent, (2-MeTHF) was employed for the polymer synthesis. [ABSTRACT FROM AUTHOR]