T:Toxic;
117-81-7Relevant academic research and scientific papers
Endocrine activities of phthalate alternatives; Assessing the safety profile of furan dicarboxylic acid esters using a panel of human cell based reporter gene assays
Van Vugt-Lussenburg, Barbara M. A.,Van Es, Daan S.,Naderman, Matthijs,Le Notre, Jerome,Klis, Frits Van Der,Brouwer, Abraham,Van Der Burg, Bart
, p. 1873 - 1883 (2020)
FDCA esters are highly relevant biobased alternatives for currently used benzene dicarboxylic acid esters. Despite all the developments on 2,5-FDCA applications, to the best of our knowledge thus far no toxicological data were available for 2,5-FDCA esters. In the present study we aimed to fill this gap, by using an in vitro reporter gene assay approach to compare the activity profile of commonly used phthalates to that of their furan-based counterparts. The assay selection was aimed at the detection of endocrine activity, since several phthalates are heavily scrutinised for their endocrine disrupting properties. However, to avoid missing other relevant toxicological endpoints, several assays able to detect various forms of cellular stress were also included in the panel. The results showed that the (ortho)benzene dicarboxylic acid esters were predominantly active on several of the endocrine assays. In comparison, six of the seven furan dicarboxylic acid based diesters tested here showed no activity in any of the 13 assays used. Only the isobutyl derivative DIBF showed moderate estrogenic activity on one assay, compared to much more pronounced activities on four assays for the ortho-phthalate analogue. Overall, the results presented in this paper are a strong indication that 2,5-FDCA based diesters in general are not only technically viable alternatives to phthalates, but also offer significant toxicological benefits, which supports a non-regrettable substitution.
Municipal solid waste incineration bottom ash: Characterization and kinetic studies of organic matter
Dugenest,Combrisson,Casabianca,Grenier-Loustalot
, p. 1110 - 1115 (1999)
Bottom ash is the main solid residue (in weight) which is produced by municipal solid waste incineration (MSWI) facilities. To be reused in public works, it has to be stored previously a few months. This material is composed primarily of a mineral matrix but also contains unburnt organic matter. The mineral content and its change in the course of aging are relatively well- known, in contrast with the organic content. So in order to detect the phenomena responsible for changes in organic matter and their effects during aging, the concentrations of the main organic compounds previously characterized, the number of microorganisms, and the release of carbon dioxide were followed kinetically (over 13 months) in model laboratory conditions (mass, particle size, humidity, temperature, aerobiosis). The results showed that the aging process led to the natural biodegradation of the organic matter available in bottom ash, composed essentially of carboxylic acids and n-alkanes (steroids and PAH's to a lesser extent), and consequently that it would improve the bottom ash quality. Furthermore these results were confirmed by the study of aging Conducted in conditions used in the industrial scale (over 12 months).
A novel hydrogen-bonded silica-supported acidic ionic liquid: An efficient, recyclable and selective heterogeneous catalyst for the synthesis of diesters
Fareghi-Alamdari, Reza,Niri, Mehri Nadiri,Hazarkhani, Hassan
, (2018)
Abstract: In this study, two novel acidic ionic liquids, including a hydroxyl functionalized diacidic ionic liquid [HFDAIL] and a sulfonated diacidic ionic liquid [SFDAIL], were prepared and immobilized on the surface of silica nanoparticles (SNPs) via hydrogen bonding. The materials were characterized by FT-IR, NMR, SEM, nitrogen physisorption measurement, TGA and acid-base titration. The catalytic activity of the prepared catalysts was investigated in the synthesis of phthalate, maleate and succinate diesters under solvent-free conditions. It was found that nanosilica@[HFDAIL] with higher availability of acidic sites and higher hydrophilicity was more efficient compared to the nanosilica@[SFDAIL]. Notably, nanosilica@[HFDAIL] catalyst has also demonstrated excellent selectivity for the diester product while the monoester product was predominant in the case of nanosilica@[SFDAIL] even after prolonged reaction time or higher catalyst loading. In addition, the nanosilica@[HFDAIL] catalyst could be separated by simple filtration and reused several times without any significant loss of catalytic performance, but a remarkable decrease in activity was observed for nanosilica@[SFDAIL] in the next runs. GRAPHICAL ABSTRACT?: SYNOPSIS Two novel acidic ionic liquids, including a hydroxyl functionalized diacidic ionic liquid [HFDAIL] and a sulfonated diacidic ionic liquid [SFDAIL], were prepared and immobilized on the surface of silica nanoparticles via hydrogen bonding. The catalytic activity of the catalysts was investigated in the synthesis of diesters under solvent-free conditions.
Catalytic upcycling of PVC waste-derived phthalate esters into safe, hydrogenated plasticizers
Bals, Sara,De Vos, Dirk E.,Diefenhardt, Thomas,Jain, Noopur,Marquez, Carlos,Schlummer, Martin,Windels, Simon
supporting information, p. 754 - 766 (2022/02/02)
Recycling of end-of-life polyvinyl chloride (PVC) calls for solutions to deal with the vast amounts of harmful phthalate plasticizers that have historically been incorporated in PVC. Here, we report on the upcycling of such waste-extracted phthalate esters into analogues of the much safer diisononyl 1,2-cyclohexanedicarboxylate plasticizer (DINCH), via a catalytic one-pot (trans)esterification-hydrogenation process. For most of the virgin phthalates, Ru/Al2O3 is a highly effective hydrogenation catalyst, yielding >99% ring-hydrogenated products under mild reaction conditions (0.1 mol% Ru, 80 °C, 50 bar H2). However, applying this reaction to PVC-extracted phthalates proved problematic, (1) as benzyl phthalates are hydrogenolyzed to benzoic acids that inhibit the Ru-catalyst, and (2) because impurities in the plasticizer extract (PVC, sulfur) further retard the hydrogenation. These complications were solved by coupling the hydrogenation to an in situ (trans)esterification with a higher alcohol, and by pretreating the extract with an activated carbon adsorbent. In this way, a real phthalate extract obtained from post-consumer PVC waste was eventually completely (>99%) hydrogenated to phthalate-free, cycloaliphatic plasticizers. This journal is
Micro-flow nanocatalysis: synergic effect of TfOH@SPIONs and micro-flow technology as an efficient and robust catalytic system for the synthesis of plasticizers
Tashi, Maryam,Shafiee, Behnaz,Sakamaki, Yoshie,Hu, Ji-Yun,Heidrick, Zachary,Khosropour, Ahmad R.,Beyzavi, M. Hassan
, p. 37835 - 37840 (2018/11/26)
The combination of continuous flow technology with immobilizing of only 0.13?mol% of triflic acid (TfOH) on silica-encapsulated superparamagnetic iron oxide nanoparticles (SPIONs) under solvent-free conditions successfully provided a powerful, efficient, and eco-friendly route for the synthesis of plasticizers. The turnover frequency value in micro-flow conditions varied in the range of 948.7 to 7384.6 h?1 compared to 403.8 to 3099 h?1 for in-flask. This technique works efficiently, encouraging future applications of micro-flow nano-catalysis in green chemistry.
Diacidic ionic liquid supported on magnetic-silica nanocomposite: a novel, stable, and reusable catalyst for selective diester production
Fareghi-Alamdari, Reza,Nadiri Niri, Mehri,Hazarkhani, Hassan,Zekri, Negar
, p. 2615 - 2629 (2018/09/13)
Abstract: Supported diacidic ionic liquid on magnetic silica nanoparticles (SDAIL@magnetic nanoSiO2) was successfully prepared through a multi-step approach. 2,2- bis ((3- methylimidazolidin-1-yl) methyl) propane- 1,3- diol bromide salt was immobilized onto the surface of magnetic silica nanoparticles via covalent bonding to prepare a novel powerful acidic catalyst. The synthesized catalyst was characterized by FT-IR, SEM, TGA, VSM, N2 adsorption–desorption measurements and acid-base titration. The catalytic activity of the prepared SDAIL@magnetic nanoSiO2 was investigated for the selective diesterification of alcohols by phthalic anhydride to afford corresponding dialkyl plasticizers under solvent-free conditions. The nature of two acidic counter anions as well as the presence of Lewis acidic species (Fe3O4) on the magnetic nanosilica and high surface area of the nanosilica influenced the behavior of the catalyst. Surperisingly, the high acidic character of the catalyst facilitates the reaction with a short reaction time. Furthermore, TG analysis strongly demonstrates that major content of IL is still stable on the support up to 290?°C, so catalyst has a good thermal stability. Under the optimized conditions, the conversion of phthalic anhydride was 100% and diester plasticizers were obtained with excellent yields (80–100%). The SDAIL@magnetic nanoSiO2 catalyst showed a good reusability and could be easily separated from the reaction mixture using an external magnet thanks to its superparamagnetic behavior and reused for several runs without significant activity loss. An important advantage of the SDAIL@magnetic nanoSiO2 was its high-hydrophilicity resulted in excellent selectivity towards the formation of only diesters which are commonly used plasticizers in different industries. Graphical abstract [Figure not available: see fulltext.].
Synthesis and characterization of a new hydroxyl functionalized diacidic ionic liquid as catalyst for the preparation of diester plasticizers
Fareghi-Alamdari, Reza,Nadiri Niri, Mehri,Hazarkhani, Hassan
, p. 153 - 160 (2016/12/30)
Two new functionalized diacidic ionic liquids (FDAILs) including hydroxyl functionalized diacidic ionic liquid (HFDAIL) and sulfonated diacidic ionic liquid (SFDAIL) were synthesized and characterized by 1HNMR, 13CNMR and FT-IR. The catalytic activities of these FDAILs were examined in esterification reaction of anhydrides with some alcohols to give corresponding dialkyl plasticizers under solvent-free conditions. The results indicate that HFDAIL, as hydroxyl-bearing catalyst, show better catalytic performance. Under the optimum conditions, using HFDAIL, the conversion of phthalic anhydride was high and diester plasticizers were obtained with good to excellent yields in the presence of only 10?mol% of ionic liquid. All the produced diesters could be easily recovered due to their immiscibility with the ionic liquid. Recycling experiments suggests that these ionic liquids can be reused several times without remarkable loss in their catalytic activity.
A liquid phase oxidation of O-xylene with esterification coupling preparation of phthalic acid diester method
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Paragraph 0020-0023; 0026, (2017/02/24)
The invention relates to a method for preparation of diester phthalate by o-xylene liquid-phase oxidation and esterification coupling. In the presence of a catalyst, air or oxygen is used as an oxygen source for preparation of the diester phthalate by o-xylene liquid-phase oxidation and esterification coupling. The method has the advantages of mild reaction conditions, safe operation, low raw material and energy consumption, high conversion rate and high selectivity and the like.
Nano-SO42-/TiO2catalyzed eco-friendly esterification of dicarboxylic acids
Ji, Xianbing,Chen, Yinxia,Shen, Zuoyuan
, p. 5769 - 5772 (2014/12/11)
Nano-SO42-/TiO2 was prepared by wet impregnation method. The structure and properties of the prepared nano-SO42-/TiO2catalyst was characterized by XRD, SEM, TEM and BET analysis. The catalytic activities of the catalysts were tested by the esterification of sebacic acid with 2-ethyl hexanol and a series of other dicarboxylic acid. The influence factors on the reaction, such as the catalyst calcination temperature, reaction temperature/time and the molar ratio of acid to alcohol were extensively explored. Nano-SO42-/TiO2prepared exhibited much higher catalytic activity in esterification reactions. By applying the optimized reaction condition, i.e. 160 C, 2 h, 5 wt % nano-SO42-/TiO2with a 1:3 molar ratio of sebacic acid to 2-ethyl hexanol, higher than 99 % isolated of the desired ester could be obtained.
Sulfonated graphene as highly efficient and reusable acid carbocatalyst for the synthesis of ester plasticizers
Garg, Bhaskar,Bisht, Tanuja,Ling, Yong-Chien
, p. 57297 - 57307 (2015/02/02)
Plasticizers are well known for their effectiveness in producing flexible plastics. The automotive, plastic and pharmaceutical industries, essential to a healthy economy, rely heavily on plasticizers to produce everything from construction materials to medical devices, cosmetics, children toys, food wraps, adhesives, paints, and 'wonder drugs'. Although H2SO4 is commonly used as commodity catalyst for plasticizer synthesis it is energy-inefficient, non-recyclable, and requires tedious separation from the homogeneous reaction mixture resulting in abundant non-recyclable acid waste. In this study, for the first time, we report an efficient synthesis of ester plasticizers (>90% yields) using sulfonated graphene (GSO3H) as an energy-efficient, water tolerant, reusable and highly active solid acid carbocatalyst. The hydrothermal sulfonation of reduced graphene oxide with fuming H2SO4 at 120°C for 3 days afforded GSO3H with remarkable acid activity as demonstrated by 31P magic-angle spinning (MAS) NMR spectroscopy. The superior catalytic performance of GSO3H over traditional homogeneous acids, Amberlyst-15, and acidic ionic liquids has been attributed to the presence of highly acidic and stable sulfonic acid groups within the two dimensional graphene domain, which synergistically work for high mass transfer in the reaction. Furthermore, the preliminary experimental results indicate that GSO3H is quite effective as a catalyst in the esterification of oleic and salicylic acid and thus may pave the way for its broad industrial applications in the near future.
