Design of New Cardanol Derivative: Synthesis and Application as Potential Biobased Plasticizer for Poly(lactide)

A novel biobased plasticizer made of cardanol is designed for poly(lactide) (PLA). This cardanol‐derived plasticizer, i.e., methoxylated hydroxyethyl cardanol (MeCard), is synthesized through methoxylation of the double bonds on the side chain of cardanol, and characterized by ¹H NMR and mass spectrometry. The plasticization effect of MeCard on the molecular structure, morphology, thermal and mechanical properties of PLA is evaluated and compared to that of a commercial cardanol, i.e., hydroxyethyl cardanol (pCard). The plasticization efficiency of MeCard is demonstrated by a substantial decrease of the glass transition temperature and storage modulus together with a significant increase of the elongation at break as compared to neat PLA. Moreover, MeCard exhibits higher plasticization performance than pCard toward PLA. Such behavior is related to a higher miscibility and compatibility between PLA and MeCard thanks to the methoxylation of the double bonds on the side chain of cardanol as shown by SEM micrographs.

     

Hydrolytic degradation of poly(l‐lactic acid)/poly(methyl methacrylate) blends

The hydrolytic degradation of poly(l ‐lactic acid)/poly(methyl methacrylate) (PLLA/PMMA) blends was carried out by the immersion of thin films in buffer solutions (pH = 7.24) in a shaking water bath at 60 °C for 38 days. The PLA/PMMA blends (0/100; 30/70; 50/50; 70/30; 100/0) were obtained by melt blending using a Brabender internal mixer and shaped into thin films of about 150 µm in thickness. Considering that PMMA does not undergo hydrolytic degradation, that of PLLA was followed via evolution of PLA molecular weight (recorded by size exclusion chromatography), thermal parameters (differential scanning calorimetry (DSC)) and morphology of the films (scanning transmission electron microscopy). The results reveal a completely different degradation pathway of the blends depending on the polymethacrylate/polyester weight ratio. DSC data suggest that, during hydrolysis at higher PMMA content, the polyester amorphous chains, more sensitive to water, are degraded before being able to crystallize, while at higher PLLA content, the crystallization is favoured leading to a sample more resistant to hydrolysis. In other words, and quite unexpectedly, increasing the content of water‐sensitive PLLA in the PLLA/PMMA blends does not mean de facto faster hydrolytic degradation of the resulting materials. © 2018 Society of Chemical Industry     

Encapsulation of nanoparticles by polymerization compounding in a gas/solid fluidized bed reactor

For the first time, a fluidized bed reactor was used for encapsulating nanoparticles by the polymerization compounding approach using Ziegler–Natta catalysts. The polymerization reaction was carried out using a solvent-free process in a gas-phase reactor. This direct gas–solid reaction greatly simplified collecting the particles of interest after polymerization because none of the extra steps often found in encapsulation processes, such as filtering and drying, were performed in this work. The grafting of the catalyst to the original surface of particles was confirmed by X-ray photoelectron spectroscopy. Micrographs obtained by transmission electron microscopy confirmed the presence of a thin layer of polymer, in the order of a few nanometers, around the particles. The thickness of this coating was affected by the operating conditions of the process. The characterization of the modified particles with electron microscopy also revealed that zirconia nanoparticles tend to be coated in an agglomerated state, whereas aluminum particles were mostly individually encapsulated by the polymer. In addition, the effects of temperature and pressure were studied on the encapsulation process and a kinetic analysis was presented based on the available models in the literature. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

Transport properties of organic vapours in silicone/clay nanocomposites

Poly(dimethylsiloxane) (PDMS)/clay nanocomposites have been synthesized using a novel ω-ammonium functionalized oligo-PDMS surfactant (PDMS-N⁺(CH₃)₃) and processed in membrane form. In order to relate the clay morphological structure to the degree of dispersion and physical properties of the membrane, the clay ion-exchanged by PDMS-N⁺(CH₃)₃ has been compared to a non-exchanged sodium MMT and to two organoclays organo-modified by using either non-functional alkyl ammonium cations (C₃₈H₈₀N⁺) or hydroxyalkyl ammonium (C₂₂H₄₈ON⁺) cations. Morphological analysis and transport properties (sorption, diffusion and permeability) have been investigated using two penetrants: acetone and n-hexane. The mechanical and rheological properties of the PDMS nanocomposite membranes have also been studied. It has been found a significant effect of the clay organo-modifier on the morphology, physical and barrier properties of the systems.     

Role of Orai3 in the Pathophysiology of Cancer

The mammalian exclusive Orai3 channel participates in the generation and/or modulation of two independent Ca²⁺ currents, the store-operated current, I_crac, involving functional interactions between the stromal interaction molecules (STIM), STIM1/STIM2, and Orai1/Orai2/Orai3, as well as the store-independent arachidonic acid (AA) (or leukotriene C4)-regulated current I_arc, which involves Orai1, Orai3 and STIM1. Overexpression of functional Orai3 has been described in different neoplastic cells and cancer tissue samples as compared to non-tumor cells or normal adjacent tissue. In these cells, Orai3 exhibits a cell-specific relevance in Ca²⁺ influx. In estrogen receptor-positive breast cancer cells and non-small cell lung cancer (NSCLC) cells store-operated Ca²⁺ entry (SOCE) is strongly dependent on Orai3 expression while in colorectal cancer and pancreatic adenocarcinoma cells Orai3 predominantly modulates SOCE. On the other hand, in prostate cancer cells Orai3 expression has been associated with the formation of Orai1/Orai3 heteromeric channels regulated by AA and reduction in SOCE, thus leading to enhanced proliferation. Orai3 overexpression is associated with supporting several cancer hallmarks, including cell cycle progression, proliferation, migration, and apoptosis resistance. This review summarizes the current knowledge concerning the functional role of Orai3 in the pathogenesis of cancer.     

Recent Advances in Reactive Extrusion Processing of Biodegradable Polymer‐Based Compositions

This review reports on recent advances in the design of biodegradable polymers built from petroleum and renewable resources using reactive extrusion processing. Reactive extrusion represents a unique tool to manufacture biodegradable polymers upon different types of reactive modification in a cost‐effective way. Partially based on our ongoing research, ring‐opening polymerization of biodegradable polyesters will be approached as well as the chemical modification of biodegradable polymers, particularly natural polymers. The development of environmentally friendly polymer blends as well as (nano)composites from natural polymers, including natural fibers and nanoclays, through reactive extrusion, as an efficient way to improve the interfacial adhesion between these components, will be also discussed.

     

Polylactide (PLA)—a new way of production

Poly(lactide) (PLA), a biodegradable aliphatic polyester with excellent properties for different polymer applications, has been used mostly in the biomedical field, mainly because of its high price, resulting from expensive polymerization and purification techniques. Although this polymer can play a major role in future markets for biodegradable polymers, the current high price has to be reduced significantly to at least $4 US/kg. Therefore, this paper aims to partially review the polymerization techniques traditionally used in PLA synthesis and to propose new developments that enable us to produce these polymers by an innovative process for just a portion of the costs traditionally charged, using reactive extrusion techniques in a closely intermeshing co-rotating twin screw extruder. This paper gives an overview of attainable mechanical properties and future markets.     

Use of a new natural clay to produce poly(methyl methacrylate)‐based nanocomposites

Nanocomposites of poly(methyl methacrylate) (PMMA) filled with 3 wt% of modified natural Algerian clay (AC; montmorillonite type) were prepared by either in situ polymerization of methyl methacrylate initiated by 2,2′‐azobisisobutyronitrile or a melt‐mixing process with preformed PMMA via twin‐screw extrusion. The organo‐modification of the AC montmorillonite was achieved by ion exchange of Na⁺ with octadecyldimethylhydroxyethylammonium bromide. Up to now, this AC montmorillonite has found applications only in the petroleum industry as a rheological additive for drilling muds and in water purification processes; its use as reinforcement in polymer matrices has not been reported yet. The modified clay was characterized using X‐ray diffraction (XRD), which showed an important shift of the interlayer spacing after organo‐modification. The degree of dispersion of the clay in the polymer matrix and the resulting morphology of nanocomposites were evaluated using XRD and transmission electron microscopy. The resulting intercalated PMMA nanocomposites were analysed using thermogravimetric analysis and differential scanning calorimetry. The glass transition temperature of the nanocomposites was not significantly influenced by the presence of the modified clay while the thermal stability was considerably improved compared to unfilled PMMA. This Algerian natural montmorillonite can serve as reinforcing nanofiller for polymer matrices and is of real interest for the fabrication of nanocomposite materials with improved properties. Copyright © 2009 Society of Chemical Industry     

Modeling ozone and aerosol formation and transport in the pacific northwest with the community Multi-Scale Air Quality (CMAQ) modeling system

The Community Multi-Scale Air Quality (CMAQ) modeling system was used to investigate ozone and aerosol concentrations in the Pacific Northwest (PNW) during hot summertime conditions during July 1-15, 1996. Two emission inventories (El) were developed: emissions for the first El were based upon the National Emission Trend 1996 (NET96) database and the BEIS2 biogenic emission model, and emissions for the second El were developed through a "bottom up" approach that included biogenic emissions obtained from the GLOBEIS model. The two simulations showed that elevated PM2.5 concentrations occurred near and downwind of the Interstate-5 corridor along the foothills of the Cascade Mountains and in forested areas of central Idaho. The relative contributions of organic and inorganic aerosols varied by region, but generally organic aerosols constituted the largest fraction of PM2.5. In wilderness areas near the 1-5 corridor, organic carbon from anthropogenic sources contributed approximately 50% of the total organic carbon with the remainder from biogenic precursors, while in wilderness areas in Idaho, biogenic organic carbon accounted for 80% of the total organic aerosol. Regional analysis of the secondary organic aerosol formation in the Columbia River Gorge, Central Idaho, and the Olympics/Puget Sound showed that the production rate of secondary organic carbon depends on local terpene concentrations and the local oxidizing capacity of the atmosphere, which was strongly influenced by anthropogenic emissions. Comparison with observations from 12 IMPROVE sites and 21 ozone monitoring sites showed that results from the two El simulations generally bracketed the average observed PM parameters and that errors calculated for the model results were within acceptable bounds. Analysis across all statistical parameters indicated that the NW-AIRQUEST El solution performed better at predicting PM2.5, PM1, and beta(ext) even though organic carbon PM was over-predicted, and the NET96 El solution performed better with regard to the inorganic aerosols. For the NW-AIRQUEST El solution, the normalized bias was 30% and the normalized absolute error was 49% for PM2.5 mass. The NW-AIRQUEST solution slightly overestimated peak hourly ozone downwind of urban areas, while the NET96 solution slightly underestimated peak values, and both solutions over-predicted average 03 concentrations across the domain by approximately 6 ppb.