Abstract This work reports the preparation of magnetic polymeric microspheres based on poly(methyl methacrylate) and the investigation of these materials as catalysts in heterogeneous Fenton processes for the decolorization of methyl orange (MO). The microspheres were prepared by polymerization of the magnetic material together with the monomers by aqueous suspension polymerization. The microspheres had specific surface area of 48.2 m2 g-1. Mossbauer data indicated that the magnetic material was a mixture of magnetite (31%), maghemite (21%), and goethite (48%). Fenton reactions were performed by varying the concentration of H2O2, pH, composite mass, and contact time. The highest color removal rates (around 80%) were reached at pH 3.0, 20% w/v of composite, 20 minutes contact time, and 10 ppm of H2O2. The composite could be reused during four cycles with removal efficiency above 50%. The results indicated that the adsorption and oxidation mechanisms act together determining the variation of the MO dye removal.

The aims of this work were to develop a magnetic carrier system consisting of microspheres made of gelatin for controlled release of doxorubicin and to investigate the ability of fructose, glucose, genipin and 1-ethyl-3(3-dimethylaminopropyl)carbodiimide (EDC) as crosslinking agents of gelatin microspheres. In addition, we also investigated the changes in the microspheres’ magnetic properties produced by using magnetite incorporated by three different methods and the doxorubicin release performance by using a constant, oscillating or no external magnetic field. The system obtained with fructose as crosslinker (low toxicity) was superparamagnetic, with high saturation magnetization and release profiles that could be controlled. Among the crosslinkers studied, genipin was the most efficient to reduce the solubility of the gelatin microspheres in water. When ferrous chloride was employed in magnetite synthesis, the Ms showed the highest values (61.6 emu/g), and its use in magnetic gelatin microspheres allowed the production of systems with high magnetization (29.6 emu/g).

Abstract Preparation and characterization of polymeric microspheres based on poly(methacrylic acid-co-divinylbenzene) (P(MAA-co-DVB)) by precipitation polymerization are reported. The influence of the change in comonomer composition, crosslinking degree, ratio of total monomers/diluents by weight/volume (g/100 mL) and the volume ratio of diluents were studied. Spherical particles were obtained in the range from 1.42 to 8.41 µm. An increase in particle size and thermal resistance with decreasing molar fraction of methacrylic acid (MAA) were observed, associated with increases in critical chain length (CCL) and the number of crosslinks in this system, respectively. The analysis of particles with molar fraction of 50% MAA and acetonitrile/toluene volumetric ratio of 75/25 showed that larger particle size and yield were achieved with increasing ratio of total monomers/diluents (g / 100 mL). The particles prepared with 14% molar fraction of MAA obtained greater swelling ratios than the particles prepared with 50% MAA.

Abstract Core-shell magnetic polymer particles were synthesized by seeded suspension polymerization. The core was made of poly(methyl methacrylate-co-divinylbenzene) and a mixture of magnetite, maghemite and goethite (P(MMA-co-DVB)-M). The shell was composed of poly(glycidyl methacrylate-co-divinylbenzene) (P(GMA-co-DVB)). These particles were characterized by infrared spectrometry (FTIR), thermal analysis (TG), scanning electron microscopy (SEM), dynamic light scattering (DLS) and vibrating sample magnetometry (VSM). The results showed the formation of core-shells with good magnetic properties (≈7.1 emu/g) and good thermal resistance (≈300 ºC). The light scattering experiments showed that the particle size of these materials changed from 5-90 microns (core) to 5-120 microns (core-shell). Scanning electron microscopic images were useful to show the formation of P(GMA-co-DVB) shells on P(MMA- co-DVB)-M cores. The materials synthesized in this work have potential to be modified and employed in magnetic separation processes in the biotech and environmental fields.

Microesferas poliméricas à base de metacrilato de metila (MMA), divinilbenzeno (DVB) e material magnético foram preparadas via polimerização por suspensão. Foi estudada a influência da polimerização em suspensão ou semisuspensão, concentração de material magnético e concentração de divinilbenzeno sobre as características das microesferas obtidas. As partículas poliméricas foram caracterizadas por espectroscopia vibracional na região do infravermelho por transformada de Fourier (FT-IR), microscopia eletrônica de varredura, analisador de área específica e porosimetria, espalhamento de luz e magnetometria de amostra vibrante. O material magnético também foi caracterizado por FT-IR, além de difratometria de raios X e espectroscopia Mössbauer. Foram obtidas, com sucesso, microesferas poliméricas magnéticas à base de MMA e DVB (P(MMA-co-DVB)-M), contendo partículas magnéticas tanto na superfície quanto no interior da microesfera. As partículas obtidas através de polimerização em semisuspensão apresentaram tamanhos menores e distribuição de tamanhos de partículas mais estreita que as partículas obtidas através de suspensões convencionais. Os compósitos apresentaram um comportamento superparamagnético. As microesferas magnéticas sintetizadas neste trabalho têm potencial para serem modificadas e aplicadas como resinas de troca iônica ou suportes catalíticos.

Magnetic polymeric microspheres based on methyl methacrylate (MMA), divinylbenzene (DVB) and magnetic materials were prepared via suspension polymerization. We studied the influence of the suspension or semi-suspension polymerization, magnetic materials and divinylbenzene concentration on the characteristics of the microspheres. Polymeric particles were characterized by Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy, accelerated surface area and porosimetry analyzer (ASAP), dynamic light scattering (DLS) and vibrating sample magnetometer (VSM). The magnetic materials were also characterized by FT-IR, X-ray diffraction and Mössbauer spectroscopy. Magnetic polymeric microspheres based on MMA and DVB (P(MMA-co-DVB)-M), containing magnetic particles on the surface or inside the microspheres, were successfully obtained. The polymer particles obtained through semi-suspension polymerization had smaller sizes and narrower particle size distribution than particles obtained by conventional suspension. The composites showed a superparamagnetic behavior. The magnetic microspheres synthesized in this work have potential to be modified and applied as ion-exchange resins or catalyst supports.

O objetivo deste trabalho foi estudar sistemas catalíticos ternários constituídos por versatato de neodímio, cloreto de t-butila e hidreto de di-isobutil-alumínio para a polimerização de 1,4-cis de butadieno em hexano. Foram investigados os efeitos das razões molares Cl/Nd e Al/Nd sobre a reação de polimerização. Os polímeros foram caracterizados por cromatografia de exclusão por tamanho (SEC), espectroscopia na região do infravermelho (FT-IR) e viscosimetria no estado fundido. A atividade catalítica, massa molar, distribuição de massa molar e viscosidade Mooney foram fortemente influenciados pela variação da razão molar Cl/Nd. Os maiores teores de unidades cis foram observados em razões molares Cl/Nd > 3. O valor máximo de atividade catalítica foi obtido em razões molares Cl/Nd na faixa de 3 a 5. A microestrutura do polibutadieno foi significativamente influenciada pelo aumento da razão molar Al/Nd. Foi observado um valor máximo, 99% de unidades cis, na razão molar Al/Nd = 10. Os dados de conversão versus tempo de reação mostraram que a velocidade de polimerização aumenta com a razão molar Al/Nd alcançando um valor máximo na razão molar Al/Nd=23. As curvas de distribuição de massa molar evidenciaram um significativo processo de transferência de cadeia para os polímeros produzidos em razões Al/Nd mais altas.

This work studied ternary catalyst systems composed of neodymium versatate, t-butyl chloride and diisobutylaluminium hydride used in the cis-1,4 polymerization of butadiene in hexane. The effect of Cl/Nd and Al/Nd molar ratios on the polymerization was investigated. The polymers were characterized by size exclusion chromatography (SEC), Fourier transform infrared spectroscopy (FT-IR) and viscosimetry in melted-state. The catalytic activity, molecular weight, molecular weight distribution and Mooney viscosity were strongly influenced by the Cl/Nd molar ratio. The highest cis contents were observed at Cl/Nd molar ratio > 3. The maximum of catalytic activity was obtained at Cl/Nd molar ratios between 3 and 5. The microstructure of polybutadiene was significantly influenced by the increase in the Al/Nd molar ratio. The maximum value, 99% of cis content, was observed for the Al/Nd molar ratio = 10. The conversion data versus reaction time showed that the rate of polymerization increases with the Al/Nd molar ratio reaching a maximum in Al/Nd = 23. The molecular weight distribution curves showed a significant chain transfer process for polymers produced at higher Al/Nd molar ratios.

O objetivo deste trabalho foi estudar sistemas catalíticos ternários constituídos por versatato de neodímio, cloreto de t-butila e hidreto de di-isobutil-alumínio para a polimerização de 1,4-cis de butadieno em hexano. Foi investigado o efeito do envelhecimento natural do catalisador (1 a 60 dias a 8,5°C) sobre a conversão, a atividade catalítica e a micro- e macroestrutura do polibutadieno. Foi estudado também o efeito do envelhecimento forçado (40°C), das diferentes fases do preparo do catalisador sobre as características da polimerização e do polímero sintetizado. Os polímeros foram caracterizados por cromatografia de exclusão por tamanho (SEC), espectroscopia na região do infravermelho (FT-IR), viscosimetria em solução e no estado fundido. O envelhecimento forçado das diferentes fases do catalisador (F1, F2, F3 e F4) afetou a conversão e a atividade catalítica de maneiras distintas. Os resultados de conversão e atividade catalítica mostraram que a fase mais afetada pelo envelhecimento forçado a 40°C foi a F1, etapa em que o versatato de neodímio é adicionado à solução de hidreto de di-isobutil-alumínio (Catalisador 447). A microestrutura não se alterou com o envelhecimento natural do catalisador enquanto que a macroestrutura mostrou dependência desta variável. Foi observado um ligeiro aumento na conversão e na atividade catalítica à medida que o tempo de envelhecimento do catalisador aumentou de 1 para 10 dias.

This work studied ternary catalyst systems composed of neodymium versatate, t-butyl chloride and diisobutyl-aluminium hydride used in the cis-1,4 polymerization of butadiene in hexane. The effect of natural aging of the catalyst (1 to 60 days at 8.5°C) on the conversion, catalyst activity and on the micro and macrostructure characteristics of polybutadiene was investigated. The effect of forced aging by heating (40°C), of the different phases of the catalyst preparation on the polymerization characteristics and the synthesized polymer was also studied. The polymers were characterized by size exclusion chromatography (SEC), Fourier transform infrared spectroscopy (FT-IR) and viscosimetry in solution and melted-state. Accelerated aging of the different phases of the catalyst (F1, F2, F3 and F4) affected the conversion and the catalytic activity in distinct ways. The results of the conversion and catalytic activity showed that F1 was the most affected phase by accelerated aging at 40°C. In this step the neodymium versatate was added to the solution of diisobutyl-aluminium hydride (Catalyst 447). The microstructure did not change with the natural aging of the catalyst while the macrostructure showed dependence on this variable. When the catalyst aging time increased from 1 to 10 days a slight increase in the conversion and the catalytic activity was observed.

The aim of this study was to incorporate an alpha-olefin (1-hexene or 1-dodecene) in a high cis polybutadiene chain, using a neodymium versatate/diisobutylaluminum hydride/t-butyl chloride catalyst system. The influence of alpha-olefin on polymerization reaction and polymer characteristics, using different weight ratios of butadiene/α-olefin, was evaluated. The copolymers were characterized by SEC, FTIR, NMR, TGA and viscosimetric analysis. The thermal stability of the polymer tended to increase with incorporation of alpha-olefins, while its microstructure was not affected. The weight average molecular mass (Mw) tended to increase and the polymerization conversion tended to decrease with increasing alpha-olefins content. The copolymers showed a lower intrinsic viscosity than for the homopolymer. The results indicated that the alpha-olefins were incorporated in the polybutadiene chain.

O objetivo deste trabalho foi estudar o efeito do tempo de envelhecimento natural do sistema catalítico versatato de neodímio/hidreto de di-isobutilalumínio/cloreto de t-butila sobre a polimerização de 2-metil, 1,3-butadieno (isopreno). Foram avaliadas a atividade catalítica e conversão, além da massa molar, distribuição de massa molar e microestrutura dos polímeros. Foi objetivo estudar também as características micro e macroestruturais do poli-1,4-cis-isopreno ao longo da polimerização. Os catalisadores envelhecidos apresentaram tempos mais curtos ao longo da polimerização e uma conversão mais alta em relação ao catalisador não envelhecido. Estes resultados em conjunto com a menor atividade catalítica nos catalisadores envelhecidos sugerem a provável desativação de alguns sítios ativos mais sensíveis. Não foi observada influência do envelhecimento do catalisador sobre a microestrutura do polímero. Houve também aumento da massa molar e estreitamento na polidispersão conforme o aumento da conversão.

The goal of this work was to study the aging effects of the catalytic system neodymium versatate/diisobutylaluminium hydride/t-butyl chloride on 2-methyl, 1.3-butadiene (isoprene) polymerization. The catalytic activity, conversion and polymer characteristics (molar mass, molar mass distribution and microstructure) were evaluated. The macro and microstructural characteristics of poly-1.4-cis-isoprene along the polymerization were also studied. The aged catalysts have shorter times along the polymerization and a higher conversion than the non-aged catalyst. Together with the lower catalytic activity for aged catalysts, these results point to possible disabling of the most sensitive active sites. Aging of the catalyst did not affect the polymer microstructure. As the conversion progressed, the molar mass increased with a narrowing in the molecular weight distribution.