In this work, dense membranes from aqueous dispersions of poly(urethane‐urea) (PUU) based on poly(propylene glycol) (PPG) and a block copolymer composed of poly(ethylene glycol) (PEG) and poly(propylene glycol) (PPG), EG‐b‐PG, with 7 wt % of the former were obtained. Nonpolluting formulations were synthesized with proportions of PPG and EG‐b‐PG as 1:0, 1:1, 1:3, and 3:1 in terms of equivalent number ratios. The effect of small and gradual increases in PEG segments was evaluated for the permeability of pure CO2, CH4, and N2, at room temperature. Slight increases in PEG‐based segments in PUU promoted some remarkable properties, which led to a simultaneous increase in CO2 permeability and ideal selectivity for CH4 (300%) and N2 (380%). Infrared spectroscopy showed that the PEG portions induced hydrogen bonds between NH of urethane and ether groups in the PEG portions, which promoted ordering of the flexible segments, confirmed by X‐ray diffractometry and small‐angle X‐ray scattering. Diffractometry techniques also confirmed the absence of crystalline domains, as did dynamic mechanical analysis. The produced membranes showed performance above Robeson's 2008 upper bound and seemed to be a superior polymeric material for CO2/CH4 and CO2/N2 separation. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 46003.
Resumo: 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 (CO 2 ) 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 (CO 2 ). 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 CO 2 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. Palavras-chave: Poliuretanos, dispersões aquosas, argila, montmorilonita, membranas, permeabilidade a gases, propriedades de barreira. Evaluation of Carbon Dioxide Gas Barrier Properties of Membranes Obtained from Aqueous Dispersions Based on Polyurethane and ClayAbstract: 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 (CO 2 ) 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 (CO 2 ). 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 CO 2 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.
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