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Formulações de aplicação não-poluente à base de poliuretanos em dispersão aquosa (WPUs), com adição de argila montmorilonita hidrofílica (CWPUs), foram sintetizadas. A permeabilidade ao dióxido de carbono (CO2) de membranas densas obtidas a partir do espalhamento das dispersões foi avaliada. Os reagentes empregados na síntese dos materiais foram: poli(glicol proplilênico) (PPG), copolímero em bloco à base de segmentos de poli(glicol etilênico) e poli(glicol propilênico) (EG-b-PG), ácido dimetilolpropiônico (DMPA), diisocianato de isoforona (IPDI) e etilenodiamina (EDA), como extensor de cadeia, levando à formação de ligações de ureia. Diferentes formulações foram obtidas variando-se a proporção de segmentos à base de poli(glicol etilênico) (PEG) e o teor de argila (0,5 e 1 %). As dispersões foram avaliadas em termos de teor de sólidos e viscosidade aparente. As membranas foram caracterizadas por espectrometria na região do infravermelho (FTIR) e permeabilidade ao dióxido de carbono (CO2). A influência nas propriedades de barreira, conferida pela presença da argila e do copolímero em bloco, foi verificada por ensaios de permeabilidade. A permeabilidade ao CO2 aumentou com o aumento no teor segmentos de PEG e diminuiu com a inserção da argila, uma vez que esta é impermeável a gases, formando caminhos preferenciais na matriz polimérica que retardam a difusão das moléculas de gás. Non-polluting aqueous polyurethane-based dispersions were synthesized in the presence and absence of montmorillonite hydrophilic clay (WPUs and CWPUs, respectively). The permeability of carbon dioxide (CO2) through dense membranes obtained from the dispersions was evaluated. The reagents used in the synthesis of the materials were: poly(propylene glycol) (PPG), block copolymer of poly(ethylene glycol) and poly(propylene glycol) (EG-b-PG), dimethylolpropionic acid (DMPA), isophorone diisocyanate (IPDI) and ethylene diamine (EDA) as chain extender, leading to the formation of urea linkages. The proportion of poly(ethylene glycol) (PEG) segments and clay content (0.5 and 1%) was varied in the formulations. The dispersions were evaluated in terms of solids content and apparent viscosity. The membranes were characterized by infrared spectrometry (FTIR) and permeability to carbon dioxide (CO2). The influence on the gas barrier properties, imparted by different contents of PEG segments in polyurethane chains, and by the clay in the formulations was verified. The permeability of CO2 increased with increasing amounts of PEG segments and decreased with the insertion of clay, since the latter is impermeable to gas and forms, in the polymeric matrix, tortuous pathways that retard gas diffusion.

Binary blends of high density polyethylene (HDPE) and oligobetapinene (OBP) were prepared by melt mixing. The morphology, thermal and permeability properties of compression molded and slow cooled films are reported. Applying the first-derivative procedure on differential scanning calorimetry (DSC) traces, we have detected the temperature of glass transition (Tg) of HDPE as a large peak centered from −125 to −100°C. In the blends, we observed that the OBP molecules were able to resolve the transition into two components. The lower one was ascribed to the γ-transition of HDPE, and the upper one was attributed to its Tg. The OBP molecules also formed another transition at a higher temperature. The blends were composed at least of three distinct phases, likely composed of amorphous HDPE with some amount of OBP molecules, amorphous OBP with some polyolefin and crystalline HDPE. The scanning electron microscopy (SEM) investigations revealed segregation of the components. The permeation to CO2 of plain HDPE and 90/10 blends was similar, but at higher concentrations of oligomer, the value was slightly higher than that of neat HDPE. The decrease of overall crystallinity was counterbalanced by the presence of an OBP rich phase in the blend and could explain the slight increase in permeability of the film blends. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 315–320, 2004

The performance of dense membranes based on anionic poly(urethane-urea) aqueous dispersions were evaluated. The materials' selectivity and permeability for CO 2 and N 2 were determined. The aqueous dispersions were prepared in four steps. The prepolymers based on hydroxyl-terminated polybutadiene (HTPB), isophorone diisocyanate (IPDI), poly(propylene glycol) (PPG) and dimethylolpropionic acid (DMPA) were synthesized in bulk. After neutralizing with triethylamine (TEA), the dispersion in water was carried out, followed immediately by chain extension reaction with ethylene diamine (EDA). The dense membranes obtained from films cast from aqueous dispersions provided higher permeability and selectivity to CO 2 as both HTPB content and the length of PPG soft segment increased and hard segment content decreased.

Mechanical, thermal, and morphological properties of blends of high density polyethylene and poly(ethylene-co-1-octene) (PEO) were evaluated. The blends were prepared in a single screw extruder at 230°C and 50 rpm with volume fraction of elastomer varying in the range from 0.05 to 0.8. Factors such as chemical similarity and melt viscosity favor the interdiffusion process of phases, resulting in better interfacial adhesion. A synergistic effect on the strength at break and elongation at break for a particular range of blend composition was observed. Blends with a volume fraction of PEO higher than 5% presented a super tough behavior at room temperature. Thermal analysis showed that there is a certain degree of interaction between high density polyethylene and PEO. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1991–1995, 2001

A pervaporação, que é um dos processos com membranas empregado em separações seletivas específicas, como misturas azeotrópicas, misturas diluídas e misturas orgânicas, tem despertado um grande interesse nos últimos anos. Neste trabalho foram estudadas a influência de parâmetros, tais como concentração da solução polimérica, tempo de exposição, concentração de aditivo e temperatura de tratamento térmico na preparação de membranas assimétricas de poliacrilonitrila. Em função destes parâmetros, as membranas foram observadas por microscopia eletrônica de varredura (MEV), e determinada a cinética de precipitação em experimentos de transmissão de luz. Os resultados mostram que a precipitação é instantânea. As membranas compostas de poliacrilonitrila, obtidas pelo espalhamento de uma solução diluída de poli(álcool vinílico) sobre as membranas assimétricas de poliacrilonitrila, foram caracterizadas na separação de misturas de água/etanol por pervaporação. Os resultados foram comparados com a membrana comercial da GFT de poli(álcool vinílico)/poliacrilonitrila.

O desenvolvimento de sistemas não-poluentes tem sido cada vez mais necessário para atender às exigências ambientais. Neste trabalho foram sintetizadas formulações de poliuretanos à base de água para a obtenção de membranas densas cujas propriedades mecânicas e de permeação a CO2 e N2 foram avaliadas. Foram empregados como monômeros polibutadieno líquido hidroxilado (HTPB), poli(glicol propilênico) (PPG), diisocianato de isoforona (IPDI) e ácido dimetilolpropiônico (DMPA). Os grupos carboxílicos foram neutralizados com trietilamina (TEA) e o extensor de cadeia utilizado foi a etilenodiamina (EDA). As membranas foram obtidas como filmes vazados a partir das dispersões aquosas. Os resultados mostraram que o aumento no teor de HTPB na formulação levou a uma maior resistência mecânica bem como a um aumento na permeabilidade e na seletividade das membranas a CO2. The performance of dense membranes based on nonpolluting systems of polyurethane aqueous dispersions was evaluated. The mechanical properties and the selectivity and permeability to CO2 and N2 were determined. The aqueous systems were based on hydroxyl-terminated polybutadiene (HTPB), poly(propylene glycol) (PPG), isophorone diisocyanate (IPDI), and dimethylolpropionic acid (DMPA). The membranes obtained from cast films provided higher permeability and selectivity to CO2 as the HTPB content increased. The tensile strength and the modulus values of the materials increased and the elongation decreased with higher amounts of HTPB. As a result, the presence of HTPB improved the mechanical resistance, the permeability and the selectivity to CO2 of the polyurethane membranes.

Quenched thin films (about 100 microns thick) of high-density polyethylene (HDPE) / oligobetapinene (OBP) blends were prepared by melt mixing with the amount of OBP varying from 0 to 40%. The results of CO 2 permeation, thermal behavior and morphology are reported. From -130 to -100 °C we observed two peaks in DSC measurements, the lower one being ascribed to γ-transition of HDPE. The upper one attributed to Tg which was shift at high contents of OBP. The OPB molecules also displayed another transition at higher temperatures. The normalized degree of crystallinity of HDPE remained constant while the overall crystallinity of the blends was reduced in all blends. We have hypothesized that three distinct phases coexist, viz. a HDPE-amorphous phase with some amount of OBP molecules, OBP-amorphous phase with polyolefin and HDPE-crystalline phases. The permeation test revealed a decrease in permeability to CO 2 independent of the amount of OBP in the blends. The reduction of gas permeation could be explained mainly by the rigidity of the OBP rich phase that has counterbalanced the decrease of overall crystallinity of the film blends.

Copolymers of styrene and vinyl acetate were synthesized electrochemically. The reaction system was composed of methylene chloride as the solvent, and a quaternary ammonium salt as the electrolyte. The reactions were run in a divided cell and the influence of current strength, reaction time, and temperature on the yield, molecular weight, and chemical composition of the resulting copolymers was investigated. It was found that the polymer chains were composed mainly of styrene units.