Polymer/layered silicate nanocomposites by combined intercalative polymerization and melt intercalation: a masterbatch process

Poly(ε-caprolactone) (PCL) and poly(vinyl chloride) (PVC) layered silicate nanocomposites were prepared by combination of intercalative polymerization and melt intercalation. In a first step, high clay content PCL nanocomposites were prepared by in situ polymerization of ε-caprolactone intercalated between selected organo-modified silicate layers. The polymerization was catalyzed with dibutyltin dimethoxide in the presence of montmorillonites, the surface of which were previously exchanged with (functionalized) long alkyl chains ammonium cations. Then, these highly filled PCL nanocomposites were added as masterbatches in commercial PCL and PVC by melt blending. The intercalation of PCL chains within the silicate layers by in situ polymerization proved to be very efficient, leading to the formation of intercalated and/or exfoliated structures depending on the organo-clay. These masterbatches were readily dispersed into the molten PCL and PVC matrices yielding intercalated/exfoliated layered silicate nanocomposites which could not be obtained by melt blending the matrix directly with the same organo-modified clays. The formation of nanocomposites was assessed both by X-ray diffraction and transmission electronic microscopy. Interestingly, this so-called ‘masterbatch’ two-step process allowed for preparing PCL nanocomposites even with non-modified natural clay, i.e. sodium montmorillonite, which showed a material stiffness much higher than the corresponding microcomposites recovered by direct melt intercalation. The thermal stability of PCL nanocomposites as a function of clay content was investigated by thermogravimetry (TGA).     

Apatitic calcium phosphates used in compression: rationalization of the end-use properties

Different apatitic calcium phosphates used as direct compression excipients have been developed in the last years. The difficulty to obtain reproducible synthesis explains their approximative and irregular composition. TRI-TAB® commercial grade called anhydrous tricalcium phosphate is associated to a chemical formula corresponding to a mixture of tricalcium phosphate (Ca₃(PO₄)₂) and calcium hydroxide (Ca(OH)₂). The chemical analysis shows that it is hydroxyapatite (Ca₁₀(PO₄)₆(OH)₂).

The purpose of this work is to rationalize the chemical and physical natures of apatitic calcium phosphates used in direct compression, and thus their technological properties. Apatitic calcium phosphates differing in their Ca/P molar ratio (from 1.500 i.e. tricalcium phosphate to 1.667 i.e. hydroxyapatite) have been synthesized and their compression properties have been analysed. The results have been compared to those of TRI-TAB®. They pointed out the importance of the chemical nature contribution. Tricalcium phosphate-based materials exhibited an excellent compactibility when not calcined. Uncalcined hydroxyapatite had similar properties than TRI-TAB®, that is intermediate. Calcined tricalcium phosphate and hydroxyapatite showed a low compaction ability. It appears that the perfect chemical and physical control of the material is important in particle design to rationalize and optimise the tablet formulation as well as the process.     

Diastereoselective Heterogeneous Catalytic Hydrogenation of Aromatic or Heteraromatic Compounds

The diastereoselective hydrogenation catalyzed by heterogeneous metallic catalysts uses a covalently bound chiral auxiliary to induce the chirality. It remains an active synthetic methodology in the asymmetric synthesis of chiral products and may proceed with high diastereoselectivity. This review describes recent examples using this method, such as hydrogenation of C=C, C=O, and C=N bonds. The use of a chiral auxiliary group has also been successfully applied to the hydrogenation of aromatic and heteroaromatic rings. The choice of the chiral auxiliary was found to play a key role in the asymmetric hydrogenation. The results could be explained in terms of steric effect, with a preferred conformation of the adduct substrate and the addition occurring from the less bulky side. The catalytic metal, the support and the presence of additives were also found to have a significant influence.     

Superheated Steam Drying: An Overview of Pilot and Industrial Dryers with a Focus on Energy Efficiency

According to the principle of sustainability, modern industry should preserve nonrenewable energy sources and develop more efficient processes, especially in terms of energy consumption. The depletion of fossil energy reserves, the environmental impact of greenhouse gases, and the possible threats of environmental taxes are the main reasons to develop new processes in general, and new drying processes in particular, for the existing industries. Using superheated steam as a drying medium instead of hot air can improve the energy efficiency by reusing the energy from exhausted steam and prevent gas emission into the atmosphere by condensation. The present review is focused on both lab-scale pilots—including impingement jet, fluid bed, kiln, fixed bed, and flash drying—described in the literature and existing industrial facilities, with a specific analysis focused on energy efficiency. The usefulness of superheated steam drying pilots for experimental research and for the design of industrial dryers is analyzed. The impact on quality specifications of the dried product for different operating conditions is also presented. Documentation on industrial superheated steam dryers is very rare. Nevertheless, this work presents and analyses the key data available for superheated steam drying of beet, alfalfa, industrial pulp, and paint sludge. Energy recovery and process integration, with a focus on specific technological challenges for industrial dryer implementation, are also presented. This document will result in a discussion of some new ideas for possible R&D in superheated steam drying.     

Thioacidolysis of Lignin: Comparison with Acidolysis

Abstract

Arylglycerol-ether bonds of lignin samples or model compounds vera selectively cleaved by treatment with dioxane-ethanethiol (9/1, v/v) and 0.2 N HBF₄ etherate or 0.2 N BF₃ etherate at 100°C for four hour3. Monomers resulting from “thioacidolysis” were identified by gas chroraatography-mass spectrometry of their trimethylslly derivatives. Compared to acidolysls (dloxane-water, 0.2 N HCL, 100°C 4h), thioacidolysis yields less complex mixtures of monomers. The monomer yields for lignin thioacidolysis were also higher than for acidolysls. This increase was particularly evident for hardwood lignins.     

Structure and Reactivity of Spruce Mechanical Pulp Lignins Part I. Bleaching and Photoyellowing of in situ Lignins

This paper reports the structural investigation of a series of in situ spruce lignins in wood, thermomechanical pulp (TMP) and the corresponding bleached (BTMP) and photoyellowed (YBTMP) samples. This was achieved by using an original two-step degradative technique, thioacidolysis followed by Raney nickel desulfuration. The determination of thioacidolysis monomeric and dimeric products allowed an estimate of various lignin building units and interunit bonds, respectively. It was observed that the thermomechanical and bleaching treatments did not affect spruce lignin structure to an appreciable extent. On the contrary, the photoyellowing treatment caused marked structural changes in lignin, particularly when run in severe conditions. These changes were essentially a decrease in the amount of β-O-4 and β-1 interunit bonds and a relative increase in catechol units and in vanillin end-groups.     

Recent advances on ion-imprinted polymers

Selective recognition of metal ions is a real challenge for a large range of applications in the analytical field (from extraction to detection and quantification). For that purpose, ion-imprinted polymers (IIPs) have been increasingly developed during the last 15 years on the principle of molecularly imprinted polymers (MIPs). Those imprinted materials are designed to mimic the binding sites of biological entities and assure an improved recognition of the template species. The aim of this review is to give the current state of the art in the conception of IIPs from the components to the polymerization process. Some applications of those materials will be also discussed.     

Implicit Bayesian Inference Using Option Prices

Abstract. A Bayesian approach to option pricing is presented in which posterior inference about the underlying returns process is conducted implicitly via observed option prices. A range of models allowing for conditional leptokurtosis, skewness and time‐varying volatility in returns are considered, with posterior parameter distributions and model probabilities backed out from the option prices. Models are ranked according to several criteria, including out‐of‐sample predictive and hedging performance. The methodology accommodates heteroscedasticity and autocorrelation in the option pricing errors, as well as regime shifts across contract groups. The method is applied to intraday option price data on the S&P500 stock index for 1995. While the results provide support for models that accommodate leptokurtosis and skewness, no one model dominates when all criteria are considered.