Abstract This work aims to study the cationic miniemulsion polymerization of styrene catalyzed by iron-containing imidazolium-based ionic liquids. The polystyrenes had very high number-average molar mass around 1300 kg mol-1 at 85 °C, molar-mass dispersity close to 2.0 and glass transition temperature higher than 102 °C with average particle diameter that remained practically unchanged during the reaction, indicating that the monomer droplets correspond to the polymerization locus. First-order kinetics up to a limit conversion, along with the increase in molar mass as the temperature decreases, styrene polymerization at low temperatures and catalyst inability to polymerize monomers that react exclusively via free radical and/or anionic polymerization, indicate the cationic nature of polymerization. 1H-NMR and 13C-NMR spectra suggested the formation of polystyrene, allowing for tacticity distribution quantification: 10% isotactic, 20% atactic and 70% syndiotactic configurations. TEM micrographs confirmed the formation of spherical polymer nanoparticles and the presence of catalysts in the polymer matrix.

Abstract A novel nanoencapsulation of n-hexadecane in high molecular weight polystyrene nanoparticles for thermal energy storage was carried out by miniemulsion polymerization using an iron-containing imidazolium-based ionic liquid (IL) as catalyst. The particle size, morphology, molecular weight, and thermal performance of nanoparticles containing the phase change material (PCM) were measured by dynamic light scattering, transmission electron microscopy, gel permeation chromatography, and differential scanning calorimetry, respectively. The nanoparticles were regular spherical, with narrow size distribution and particle size ranged from 138 nm to 158 nm. The enthalpy of melting for the nanoencapsulated PCM increased from 19 J/g to 72 J/g, as the content of n-hexadecane used increased from 20 wt% to 50 wt%. In addition, the nanoparticles showed thermal reversibility after 100 thermal cycles. The high molecular weights of the polymer, up to 1800 kDa, that could be reached with this IL may have contributed positively to this thermal behavior.

Abstract Recently, the physical and chemical effects of ultrasound in polymeric materials synthesis have attracted great attention. This work presents the synthesis of novel polymeric materials by polymerization of isophorone diisocyanate with different polyols. Polymers were synthesized by step miniemulsion polymerizations, using ultrasound bath and thermostatic bath. The effects of ultrasound, temperature and polyol type were evaluated by Fourier transform infrared spectroscopy, gel permeation chromatography, dynamic light scattering and titrimetry. Polymerization under ultrasound bath showed that different reaction temperatures in the range between 50 °C and 80 °C directly influence the molecular weight of the polymers, urea/urethane formation and increase of diisocyanate consumption rate. In addition, different polyols used in polymerizations in miniemulsion had a significant effect on the characteristics of the resulting poly(urea-urethane) nanoparticles. Finally, ultrasound assisted polymerizations showed a faster diisocyanate consumption rate, but did not lead to enhanced molecular weights.

Abstract Poly(Thioether-Ester) nanoparticles synthetized via thiol-ene polymerization from a renewable castor oil monomer are produced by miniemulsion polymerization and emulsification/evaporation of pre-formed polymer. Its antioxidant activity, probably due to the oxidation of sulfide groups, is confirmed by 2,2-diphenyl-1-picryl hydrazyl (DPPH) free radical-scavenging and β-carotene/linoleic acid assays, with an amount of polymer required to reduce the initial concentration of DPPH· radicals by 50% of ~195 µg.ml-1 promoting hydrogen or electron exchange and the capability to prevent lipid peroxidation of ~55%. The results show a promising application in food packing.

Abstract Encapsulation of bioactive compounds has been carried out to improve bioavailability and to protect them against harm conditions. However, encapsulation processes are often aggressive and it is important that encapsulated substances keep their biological activity. In this work curcumin was nanoencapsulated using dichloromethane as solvent and ultrasound as dispersion device. Nanoparticles were obtained using different curcumin concentrations and encapsulants (PLLA and Eudragit S100) and the encapsulation efficiency was inferred using spectroscopic and calorimetric techniques as well as optical microscopy. Total phenolic contents and antioxidant activity tests were applied to the curcumin before and after encapsulation and also to blank polymer nanoparticles. Results demonstrated that the encapsulation process had no deleterious influence on its antioxidant activity.

RESUMO: A encapsulação de progesterona em nanopartículas de poli(hidroxibutirato-co-hidroxivalerato) (PHBV), poli (ε-caprolactona) (PCL), poli (L-ácido lático) (PLLA) e em nanopartículas blenda de PHBV/PCL e PHBV/PLLA foi investigada neste trabalho. As nanopartículas foram produzidas pela técnica de miniemulsificação/evaporação do solvente com lecitina como surfactante e foram caracterizadas em relação ao diâmetro médio em intensidade (Dz) e o índice de polidispersão (PDI), rendimento de recuperação e eficiência de encapsulação de progesterona. Possíveis interações entre progesterona e as matrizes poliméricas foram investigadas por Espectroscopia de Infravermelho por Transformada de Fourier (FTIR). Valores elevados de rendimento de recuperação (de até 102,43±1,80% para a blenda PHBV/PLLA) e eficiência de encapsulação (de até 99,53±0,04% para PCL) foram obtidos e as nanopartículas apresentaram distribuição de tamanho estreita (0,12±0,03 para PLLA). As nanopartículas de PCL (217,5±2,12nm) apresentaram diferença significativa com todas as outras formulações (P<0,05) quanto ao Dz. A interação mais evidente entre progesterona e a matriz polimérica das nanopartículas foi para a blenda PHBV / PCL, devido ao aumento na intensidade da banda localizada em 1631 cm-1.

ABSTRACT: The encapsulation of progesterone in poly (hydroxybutirate-co-hydroxyvalerate) (PHBV), poly (ε-caprolactone) (PCL), poly (L-lactic acid) (PLLA) nanoparticles and PHBV/PCL and PHBV/PLLA blend nanoparticles was investigated in this research. Nanoparticles were produced by miniemulsion/solvent evaporation technique with lecithin as surfactant and were characterized regarding to z-average diameter (Dz) and polydispersity (PDI), progesterone recovery yield and encapsulation efficiency. Possible interactions between progesterone and the polymer matrices were investigated by Fourier Transform Infrared Spectroscopy (FTIR). High recoveries (up to 102.43±1.80% for the PHBV/PLLA blend) and encapsulation efficiencies (up to 99.53±0.04% for PCL) were achieved and the nanoparticles presented narrow size distribution (0.12±0.03 for PLLA). PCL nanoparticles (217.5±2.12nm) presented significant difference with the Dz from all the other formulations (P<0.05). The most evident interaction between progesterone and the nanoparticles polymeric matrix was found to PHBV/PCL due to the increase in the intensity of the band located in 1631 cm-1.

Visando à substituição do ABS em peças cromadas, amostras de PVC e blendas de PVC/ABS, na razão mássica de 20/80, 40/60 e 60/40, foram submetidas ao pré-tratamento em solução sulfocrômica sob diferentes condições de concentração, tempo e temperatura e sendo em seguida cromadas. As modificações na superfície das peças após o condicionamento foram analisadas por microscopia eletrônica de varredura, microscopia de força atômica e rugosidade. A qualidade da deposição metálica foi avaliada por inspeção visual e teste de adesão. Os resultados mostraram que, aumentando a concentração de PVC nas peças necessitou-se de condições operacionais mais agressivas, tais como maiores temperaturas de banho, tempo de imersão e concentração de solução sulfocrômica para que ocorresse a adesão da camada metálica. De todas as condições testadas com a solução condicionante sulfocrômica no tratamento das peças de PVC e blendas PVC/ABS de 20/80 e 40/60, a concentração de 350 g/L de ácido crômico e 400 g/L de ácido sulfúrico, temperatura de 70°C e tempo de imersão de 15 minutos, ocasionou deposição do metal em toda a superfície das peças, as quais foram aprovadas nos testes de adesão e corrosão.

To replace ABS in plated objects, samples of PVC and blends of PVC/ABS, in mass ratio of 20/80, 40/60 and 60/40, were subjected to step-conditioning (etching) in sulfochromic solution, under different conditions of concentration, time and temperature, being plated in sequence. Modifications of the surface of the samples after conditioning were analyzed by scanning electron microscopy, atomic force microscopy and roughness. The quality of metal deposition was evaluated by visual inspection and adhesion tests. Results show that increasing the amount of PVC in the blend required more aggressive operational conditions to promote metallic adhesion; higher temperature, immersion time and sulfochromic solution concentration. From all tested conditions with the sulfochromic solution for the treatment of PVC, and 20/80 and 40/60 PVC/ABS blend samples, the concentration of 350 g L–1 of chromic acid and 400 g L–1 of sulfuric acid at 70 oC and immersion time of 15 minutes, resulted in the deposition of metal layers in all evaluated specimens. These were approved in adhesion and corrosion tests.

Miniemulsion homopolymerization reactions of methyl methacrylate (MMA) and styrene (STY) using poly(L-lactide) as co-stabilizer were carried out in order to prepare poly(L-lactide)/poly(methyl methacrylate) (PLLA/PMMA) and poly(L-lactide)/polystyrene (PLLA/PS) binary blend nanoparticles. The effect of PLLA concentration on methyl methacrylate (MMA) and styrene (STY) homopolymerization reactions was evaluated. It was found that the incorporation of PLLA resulted on acceleration of MMA and STY homopolymerization reactions and led to a molar mass increase of up to 70% for PS in PLLA/PS blend nanoparticles in relation to those prepared without PLLA, which can be attributed to an increase of reaction loci viscosity (gel effect). PLLA also acted as an efficient co-stabilizer, since it was able to retard diffusional degradation of droplets when no other kind of co-stabilizer was used. Two isolated Tgs were found in both PLLA/PMMA and PLLA/PS blend nanoparticles which can be associated to blend immiscibility. TEM images corroborate these results, suggesting that immiscible PLLA/PMMA and PLLA/PS blend nanoparticles could be formed with two segregated phases and core-shell morphology.