Scielo RSS <![CDATA[Polímeros]]> vol. 24 num. SPE lang. es <![CDATA[SciELO Logo]]> <![CDATA[<b>Editorial</b>]]> <![CDATA[<b>Metal nanoparticles/ionic liquid/cellulose</b>: <b>polymeric membrane for hydrogenation reactions</b>]]> Rhodium and platinum nanoparticles were supported in polymeric membranes with 10, 20 and 40 µm thickness. The polymeric membranes were prepared combining cellulose acetate and the ionic liquid (IL) 1-n-butyl-3-methylimidazolium bis(trifluoromethane sulfonyl)imide (BMI.(NTf)2. The presence of metal nanoparticles induced an increase in the polymeric membrane surface areas. The increase of the IL content resulted in an improvement of elasticity and decrease in tenacity and toughness, whereas the stress at break was not affected. The presence of IL probably causes an increase in the separation between the cellulose molecules that result in a higher flexibility and processability of the polymeric membrane. The CA/IL/M(0) combinations exhibit an excellent synergistic effect that enhances the activity and durability of the catalyst for the hydrogenation of cyclohexene. The CA/IL/M(0) polymeric membrane displays higher catalytic activity (up to 7.353 h-1) for the 20 mm of CA/IL/Pt(0) and stability than the nanoparticles dispersed only in the IL. <![CDATA[<b>Influence of the NiO nanoparticles on the ionic conductivity of the agar-based electrolyte</b>]]> NiO nanoparticles with an average size of 15 nm were prepared by a simple, reproducible and low-cost controlled method, using nickel nitrate hexahydrate (Ni(NO3)2·6H2O). These nanoparticles were added to an agar-based polymer electrolyte formula, resulting, after reflux and solution casting, in a proton conducting membrane. The highest ionic conductivity values of 5.19x10-5 S cm-1 at room temperature and 3.32x10-4 S cm-1 at 80 ºC, were obtained for the sample with 50 wt. % of acetic acid and 0.25 g of NiO. Moreover, the samples showed 75 % of transparency in the visible region, a homogeneous surface and mainly amorphous structure. All the obtained results suggest that agar-based polymer electrolyte with NiO nanoparticles are promising candidates for electrochemical devices application. <![CDATA[<b>Preparation of Ziegler-Natta catalysts for the synthesis of polypropylene/carbon nanotubes nanocomposites by <i>in situ</i> polymerization</b>]]> Aiming to improve the dispersion of carbon nanotubes (CNT) in a polymer matrix, a fourth-generation Ziegler-Natta, ZN, catalyst was prepared in the presence of CNT to synthesize nanocomposites of polypropylene (PP/CNT) by in situ polymerization. The performance of the ZN catalyst was evaluated along with the thermal (TGA and DSC) and dynamic-mechanical properties of the nanocomposites and they were compared with those of neat PP synthesized with the standard catalyst prepared without carbon nanoparticles. The thermal degradation temperature of the PP/CNT nanocomposite increased in comparison with that of neat PP. Moreover, the crystallization temperature and the degree of crystallinity sharply increased in PP/CNT materials. Finally, the storage modulus of the nanocomposite prepared by 30 min of polymerization increased, as well as the Tg. <![CDATA[<b>Effect of synthetic mica on the thermal properties of poly(lactic acid)</b>]]> Poly(lactic acid)/Somasif fluoromica nanocomposites were prepared by melt blending and their thermal properties investigated by DSC, TGA and DMA. Three different types of synthetic mica (Somasif ME-100, Somasif MAE and Somasif MPE) were used at different contents (2.5, 5.0 and 7.5 wt %). The melt blending of PLA and these micas is characterized by a considerable reduction in the matrix molecular weight, which decreases when the nanofiller content is increased. For all nanocomposites, the thermal stability increases when mica is added to the polymer, with the Somasif MPE, producing the highest increase of the degradation temperature and highest reduction of Tg. <![CDATA[<b>Effect of tamoxifen in RAFT miniemulsion polymerization during the synthesis of polymer nanoparticles</b>]]> Tamoxifen (TXF) is currently the only hormonal agent used for treatment of breast cancer. Although very effective, TXF presents low solubility in water, which affects its absorption and bioavailability. A common strategy to overcome this barrier is the formulation of a drug delivery system (DDS) in order to increase the drug stability and improve the treatment effectiveness. Reversible addition-fragmentation chain transfer (RAFT) polymerization is the most versatile method of controlled/living radical polymerization (CLRP), allowing for synthesis of well-defined polymers and being adapted to a wide range of polymerization systems. Miniemulsion polymerization is a dispersed system that is commonly used to prepare nanoparticles (NP) with 50 to 500 nm of diameter. The aim of this work was to evaluate the effect of the in situ incorporation of TXF during miniemulsion conventional and RAFT polymerizations, using methyl methacrylate (MMA) as monomer. Although the in situ addition of TXF promoted a slight reduction of the reaction rate, it did not affect the final particle size distribution of the latex or the molecular weight control exerted by the RAFT agent. The obtained results suggest that in situ incorporation of TXF during the synthesis of polymer NP via RAFT polymerization allows for production of a polymer DDS for different uses, such as the breast cancer treatment. <![CDATA[<b>Structural and thermal properties of carboxylic acid functionalized polythiophenes</b>]]> Polythiophenes functionalized with polar groups at the end of side-chain have emerged as an alternative method to obtain good compatibility between this class of conjugated polymers and electron acceptor compounds. The aim is to prevent phase segregation and to improve the efficiency of the polythiophene technological devices. However, homopolymers synthesized from thiophene rings with high polar groups at the end of the side-chain, such as hydroxyl and carboxylic acid groups, are poorly soluble in common volatile organic solvents. We report on a systematic preparation of copolymers of 3-hexylthiophene (HT) and thiophene-3-acetic acid (TAA), using different feed ratios. The chemical structures of the copolymers were confirmed by FTIR and ¹H-NMR. The TAA content in these copolymers were 33, 38 and 54 mol %. HPSEC results did not show any remarkable correlation with TAA contents in the copolymers. In contrast, the thermal analyses showed a decrease in the thermal stability and an increase in rigidity of their backbones, for the copolymers with high amounts of TAA. The solubility and optical property of copolymers were also related to the TAA contents. Thus, the properties of these copolymers can be modulated by a simple control of feed ratio of TAA in the copolymerization. <![CDATA[<b>Strategies to improve the mechanical properties of starch-based materials</b>: <b>plasticization and natural fibers reinforcement</b>]]> Biodegradable polymers are starting to be introduced as raw materials in the food-packaging market. Nevertheless, their price is very high. Starch, a fully biodegradable and bioderived polymer is a very interesting alternative due to its very low price. However, the use of starch as the polymer matrix for the production of rigid food packaging, such as trays, is limited due to its poor mechanical properties, high hidrophilicity and high density. This work presents two strategies to overcome the poor mechanical properties of starch. First, the plasticization of starch with several amounts of glycerol to produce thermoplastic starch (TPS) and second, the production of biocomposites by reinforcing TPS with promising fibers, such as barley straw and grape waste. The mechanical properties obtained are compared with the values predicted by models used in the field of composites; law of mixtures, Kerner-Nielsen and Halpin-Tsai. To evaluate if the materials developed are suitable for the production of food-packaging trays, the TPS-based materials with better mechanical properties were compared with commercial grades of oil-based polymers, polypropylene (PP) and polyethylene-terphthalate (PET), and a biodegradable polymer, polylactic acid (PLA). <![CDATA[<b>Nanostructured Polyelectrolytes Based on SPEEK/TiO<sub>2</sub> for Direct Ethanol Fuel Cells (DEFCs)</b>]]> Proton-conducting hybrid membranes consisting of poly(ether ether ketone) sulfonated (SPEEK) and titanium oxide (TiO2) were prepared using the sol-gel technique for application in direct ethanol fuel cells. The effect from TiO2 incorporation on membrane properties such as ethanol uptake, pervaporation and proton conductivity was investigated. The uptake and permeated flux decreased with increasing content of TiO2. The ethanol permeability was about one order of magnitude smaller than Nafion® 117. FTIR spectra indicated that PEEK was sulfonated and the second degradation temperature of SPEEK58 samples confirmed the titanium oxide incorporation. The proton conductivity in ethanol solution was of the order of 10-3 S cm-1 when 4 or 8 wt% TiO2 were added, and generally increased with addition of TiO2. <![CDATA[<b>Proton conductive membranes based on poly (styrene-<i>co</i>-allyl alcohol) semi-IPN</b>]]> The optimization of fuel cell materials, particularly polymer membranes, for PEMFC has driven the development of methods and alternatives to achieve systems with more adequate properties to this application. The sulfonation of poly (styrene-co-allyl alcohol) (PSAA), using sulfonating agent:styrene ratios of 2:1, 1:1, 1:2, 1:4, 1:6, 1:8 and 1:10, was previously performed to obtain proton conductive polymer membranes. Most of those membranes exhibited solubility in water with increasing temperature and showed conductivity of approximately 10-5 S cm-1. In order to optimize the PSAA properties, especially decreasing its solubility, semi-IPN (SIPN) membranes are proposed in the present study. These membranes were obtained from the diglycidyl ether of bisphenol A (DGEBA), curing reactions in presence of DDS (4,4-diaminodiphenyl sulfone) and PSAA. Different DGEBA/PSAA weight ratios were employed, varying the PSAA concentration between 9 and 50% and keeping the mass ratio of DGEBA:DDS as 1:1. The samples were characterized by FTIR and by electrochemical impedance spectroscopy. Unperturbed bands of PSAA were observed in the FTIR spectra of membranes, suggesting that chemical integrity of the polymer is maintained during the synthesis. In particular, bands involving C-C stretching (1450 cm-1), C=C (aromatic, ~ 3030 cm-1) and C-H (2818 and 2928 cm-1) were observed, unchanged after the synthesis. The disappearance or reduction of the intensity of the band at 916 cm-1, attributed to the DGEBA epoxy ring, is evidenced for all samples, indicating the epoxy ring opening and the DGEBA crosslinking. Conductivity of H3PO4 doped membranes increases with temperature, reaching 10-4 S cm-1. <![CDATA[<b>The preparation of montmorillonite/polypyrrole nanocomposites</b>: <b>the effect of surfactant incorporation on the structure and properties</b>]]> Nanocompósitos de montmorilonita/polipirrol (MMT/PPy) foram preparados a partir da polimerização in situ do pirrol na presença de argila, bentonita sódica natural, (MMT-Na+) em solução aquosa com ou sem surfactante aniônico, dodecil sulfato de sódio (SDS), utilizando-se o cloreto de ferro (III) hexahidratado (FeCl3.6H2O), como oxidante. A estrutura e propriedades dos nanocompósitos obtidos pela polimerização in situ do pirrol na presença de SDS (MMT/PPy.SDS) e sem surfactante (MMT/PPy) foram avaliadas e comparadas a partir da espectroscopia de infravermelho com transformada de Fourier (FTIR), difração de raios X (DRX), microscopia eletrônica de varredura (MEV), microscopia eletrônica de transmissão (MET), análise termogravimétrica (TG) e método padrão quatro pontas. Os difratogramas dos nanocompósitos revelaram que o espaçamento basal d001 da MMT (1,42 nm) foi alterado para valores maiores, indicando a intercalação do PPy na MMT para ambos os nanocompósitos obtidos. Os difratogramas e as imagens de MET e MEV dos nanocompósitos de MMT/PPy.SDS confirmaram que a presença do SDS na reação promoveu, além da intercalação, esfoliação parcial da argila. Os nanocompósitos MMT/PPy.SDS apresentaram condutividade elétrica (9,50 S/cm) maior do que o nanocompósito de MMT/PPy (4,44 S/cm). A presença da argila melhorou de forma significativa a estabilidade térmica do PPy.<hr/>Montmorillonite/polypyrrole (MMT/PPy) nanocomposites were prepared by the in situ polymerization of pyrrole in the presence of clay, natural sodium bentonite, (MMT-Na+) in aqueous solutions with or without an anionic surfactant, sodium dodecyl sulfate (SDS), using Iron (III) chloride hexahydrate (FeCl3.6H2O) as oxidant. The structure and properties of the nanocomposites obtained by the in situ polymerization of pyrrole in the presence of SDS (MMT/PPy.SDS) and without surfactant (MMT/PPy) were compared and evaluated by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermogravimetric analysis and the four-point probe method. The XRD patterns of the MMT/PPy composites shows that the d001 spacing in MMT (1.42 nm) was changed to higher values, indicating the intercalation of PPy on MMT for both nanocomposites. The XRD pattern, SEM and TEM images of the MMT/PPy.SDS nanocomposites confirmed that the presence of SDS in the reaction medium promoted, beyond intercalation, the partial exfoliation of the clay. The MMT/PPy.SDS nanocomposites showed electrical conductivity (9.50 S/cm) higher than the MMT/PPy nanocomposites (4.44 S/cm). The presence of the clay significantly improved the thermal stability of PPy.