RESUMEN

A polymerization methodology is reported using sulfur monochloride (S2Cl2) as an alternative feedstock for polymeric materials. S2Cl2 is an inexpensive petrochemical derived from elemental sulfur (S8) but has numerous advantages as a reactive monomer for polymerization vs S8. This new process, termed sulfenyl chloride inverse vulcanization, exploits the high reactivity and miscibility of S2Cl2 with a broad range of allylic monomers to prepare soluble, high molar-mass linear polymers, segmented block copolymers, and crosslinked thermosets with greater synthetic precision than achieved using classical inverse vulcanization. This step-growth addition polymerization also allows for preparation of a new class of thiol-free, inexpensive, highly optically transparent thermosets (α = 0.045 cm-1 at 1310 nm), which exhibit among the best optical transparency and low birefringence relative to commodity optical polymers, while possessing a higher refractive index (n > 1.6) in the visible and near-infrared spectra. The fabrication of large-sized optical components is also demonstrated.

Asunto(s)

RESUMEN

The production of elemental sulfur from petroleum refining has created a technological opportunity to increase the valorization of elemental sulfur by the creation of high-performance sulfur based plastics with improved thermomechanical properties, elasticity and flame retardancy. We report on a synthetic polymerization methodology to prepare the first example of sulfur based segmented multi-block polyurethanes (SPUs) and thermoplastic elastomers that incorporate an appreciable amount of sulfur into the final target material. This approach applied both the inverse vulcanization of S8 with olefinic alcohols and dynamic covalent polymerizations with dienes to prepare sulfur polyols and terpolyols that were used in polymerizations with aromatic diisocyanates and short chain diols. Using these methods, a new class of high molecular weight, soluble block copolymer polyurethanes were prepared as confirmed by Size Exclusion Chromatography, NMR spectroscopy, thermal analysis, and microscopic imaging. These sulfur-based polyurethanes were readily solution processed into large area free standing films where both the tensile strength and elasticity of these materials were controlled by variation of the sulfur polyol composition. SPUs with both high tensile strength (13-24 MPa) and ductility (348 % strain at break) were prepared, along with SPU thermoplastic elastomers (578 % strain at break) which are comparable values to classical thermoplastic polyurethanes (TPUs). The incorporation of sulfur into these polyurethanes enhanced flame retardancy in comparison to classical TPUs, which points to the opportunity to impart new properties to polymeric materials as a consequence of using elemental sulfur.

RESUMEN

Chemical modification of montmorillonite though popular may be expensive and environmentally noxious and can result in secondary contamination. Therefore, there is a need for eco-friendly and efficient treatment techniques. The use of thermally enhanced rice husk montmorillonite combo (TRMC) for aqueous crude oil pollution was evaluated. The physical characterization of the sorbate revealed a light crude oil. Scanning electron microscopy of TRMC and untreated montmorillonite (UM) showed efficient utilization of the pores for crude oil sequestration. Temperatures, pH, initial oil concentration, dosage of sorbent, and time were found to be significant in the batch sorption investigation. The heterogeneous surface nature of TRMC was elucidated by the Freundlich and Scatchard model analyses. The Langmuir monolayer maximum sorption capacity was 5.8 and 9.7 g/g for UM and TRMC respectively and the latter was found to be higher than most reported sorbents. The pseudo-first-order model gave better fit than pseudo-second-order, the Bangham, and the Elovich models in kinetics based on regression and chi-square analysis. Thermodynamics showed a spontaneous, feasible, endothermic, and physical sorption processes. Regeneration and reusability studies using n-hexane as eluent showed TRMC as suitable, environmental friendly sorbents for oil spill remediation.

Asunto(s)

RESUMEN

This study investigated a new area of improving the adsorption capacity of clay using corn cob as an alternative means of clay modification to the more expensive and complicated chemical treatment techniques. Kaolinite Clay (KC), Calcined corncob-kaolinite Combo (CCKC), and Corncob (CC) adsorbents were utilized. The adsorbents were characterized by Fourier Transform-Infrared (FT-IR) Spectroscopy, Scanning Electron Microscopy (SEM), X-ray fluorescence spectroscopy, and Brunauer-Emmett-Teller (BET) surface area analyzer. Batch adsorption methodology was used to investigate the effect of pH, initial metal concentration, adsorbent dose, and contact time on adsorption of Pb (II) and Cd (II). A slight increase in BET surface area of 29.31 m2/g for CCKC from 14.12 m2/g for raw KC was achieved. The trend of metal adsorption on the adsorbents was in the order CC>CCKC>KC. The Langmuir isotherm was found to present the best fit for the unmodified adsorbents while the Freundlich was applicable for CCKC indicating multilayer heterogeneous surface. The pseudo second order kinetic model was found to be suitable in the kinetic analysis. Thermodynamic studies revealed a spontaneous physical adsorption process of metal ions on CCKC. The combo adsorbent showed highest percentage desorption (>70%) of Cd and Pb ions in both acid and basic media compared to the other adsorbents. The results of the study established the efficiency of calcined corn cob kaolinite combo as suitable adsorbent for metal ions.