The Influence of Monomer Structure on the Properties of Ionogels Obtained by Thiol–Ene Photopolymerization

The influence of ene and thiol monomer structure on the mechanical and electrochemical properties of thiol–ene polymeric ionogels were investigated. Ionogels were obtained in situ by thiol–ene photopolymerization of 1,3,5-triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (TATT), 2,4,6-triallyloxy-1,3,5-triazine (TAT), diallyl phthalate (DAP), and glyoxal bis(diallyl acetal) (GBDA) used as enes and trimethylolpropane tris(3-mercaptopropionate) (TMPTP), pentaerythritol tetrakis(3-mercaptopropionate) (PETMP), and pentaerythritol tetrakis(3-mercaptobutyrate) (PETMB) used as thiols in 70 wt.% of ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMImNTf2). The mechanical strength of ionogels was studied by puncture resistance and ionic conductivity by electrochemical impedance spectroscopy. The course of photopolymerization by photo-DSC method (differential scanning calorimetry) as well as characterization of compositions and its components (by IR and UV spectroscopy-Kamlet–Taft parameters) were also studied. The resulting ionogels were opaque, with phase separation, which resulted from the dispersion mechanism of polymerization. The mechanical and conductive properties of the obtained materials were found to be largely dependent on the monomer structure. Ionogels based on triazine monomers TAT and TATT were characterized by higher mechanical strength, while those based on aliphatic GBDA had the highest conductivity. These parameters are strongly related to the structure of the polymer matrix, which is in the form of connected spheres. The conductivity of ionogels was high, in the range of 3.5–5.1 mS∙cm−1.

Synthesis, Characterization, and Study of Proton Exchange Polymer Membrane Properties of Sulfonated Copolymer Eugenol-diallyl Phthalate

Synthesis biopolymer of sulfonated copolymer eugenol-diallyl phthalate (PEGDAF), its characterization, and study of proton exchange polymer membrane properties had been done. This synthesis was conducted by eugenol and diallyl phthalate reaction to form PEGDAF, which is sulfonated using sulfuric acid. In addition, the functional groups of the PEGDAF and its sulfonated form were analyzed using FT-IR. Furthermore, the polymer properties were determined by measuring values of sulfonation degree, cation exchange capacity, proton conductivity, and water uptake. FT-IR spectra showed that the vinyl group had been added to the process of PEGDAF formation, while spectra deconvolution was used to confirm the occurrence of sulfonation reaction. The sulfonation of PEGDAF in 2 h optimum reaction time produces a black solid with a melting point of 133 °C in 16.55% yield. The highest proton conductivity, cation exchange capacity (CEC), and water uptake were 8.334 × 10–6 S cm–1, 0.44 meq/g, and 73.0%, respectively.

Degradation of Diallyl Phthalate (DAP) by Fenton Oxidation: Mechanistic and Kinetic Studies

In this work, the degradation and mineralization of Diallyl Phthalate (DAP) in water by Fenton oxidation was investigated. The effects of different experimental parameters including the initial pH, the hydrogen peroxide (H2O2) dose, the catalyst (Fe2+) dose, the iron source, and the DAP concentration on the rate and the yield of DAP degradation by Fenton oxidation were evaluated. DAP and its intermediates were quantified by high performance liquid chromatography (HPLC) analysis and the measurement of total organic carbon (TOC) during Fenton oxidation. The results obtained confirmed that hydroxyl radicals (HO•) generated from Fenton’s reaction were capable of completely eliminating DAP from water. Fenton oxidation of 100 mg/L DAP aqueous solution at pH = 3.2 required 1000 mg/L H2O2 and 50 mg/L Fe2+. Under these conditions, more than TOC removal exceeded 95% after 300 min Fenton oxidation. The competition kinetics method was used to determine an absolute rate constant of 7.26.109 M−1 s−1 for the reaction between DAP and HO• radicals. HPLC analysis showed that phthalic acid, 1,2-dihydroxybenzene, 1,2,4-trihydroxybenzene, maleic acid, formic acid and oxalic acid were the main intermediates formed during DAP degradation. Accordingly, a simple DAP degradation mechanism by the Fenton reaction was proposed. These promising results proved the potential of Fenton oxidation as a cost-effective method for the decontamination of wastewaters containing phthalates.