Addition of Di(trimethylsilyl) Phosphite to Schiff Bases of 2,5-Diformylfuran

A series of 2,5-Furanyl-bis-(aminomethylphosphonic Acids) has been synthesized by the addition of di(trimethylsilyl) phosphite to azomethine bond of achiral Schiff bases derved from 2,5-diformylfuran. The stereochemical aspect of this reaction has been studied and compared with the behaviour of achiral terephthalic Schiff bases in similar reaction. Whereas, addition to achiral terephthalic Schiff bases was found to be highly stereoselective, the analogous reaction with achiral 2,5-diformylfuran Schiff bases was stereoselective exclusively in the case when the substituent is benzyl.N/

Biodegradability and biocompatibility of copoly(butylene sebacate-co-terephthalate)s

In the present study poly (butylene sebacate-co-terephthalate)s having different compositions were synthesized with a high yield and a random distribution by thermal transesterification of poly (butylene sebacate) and poly (butylene terephthalate) homopolymers. The copolymer with the highest comonomer ratio was the least crystalline sample, although the melting peaks corresponding to both, sebacate and terephthalate-rich phases were still observable in calorimetric heating runs. This copolymer was associated with interesting thermal and mechanical properties, as the maximum melting point was higher than 100 °C and the storage modulus was also high (i.e. 1.1 × 109 N/m2 and 1.7 108 N/m2 were determined just before and after the main glass transition temperature of -12 °C). As all studied samples were thermally stable up to temperatures clearly higher than the fusion temperature, they could be easily processed. Increasing the terephthalate content of the copolymers resulted in higher hydrophobicity, which had a minor influence on cell adhesion and proliferation of both fibroblast-like and epithelial-like cells. Hydrolytic and enzymatic degradability were assessed and the effect of composition and crystallinity on the degradation rate was investigated. Molecular weight measurements during exposure to a hydrolytic media indicated a first order kinetic mechanism during the initial stages of degradation before reaching a limiting molecular size, which was indicative of solubilization. The most amorphous sample appears as a highly promising biodegradable material since it showed a significant weight loss during exposure to all selected degradation media, but also exhibited good performance and properties that were comparable to those characteristic of polyethylenePeer ReviewedPostprint (author's final draft

Synthesis of titanate nanofibers co-sensitized with ZnS and Bi2S3 nanocrystallites and their application on pollutants removal

The synthesis of nanocomposite materials combining titanate nanofibers (TNF) with nanocrystalline ZnS and Bi2S3 semiconductors is described in this work. The TNF were produced via hydrothermal synthesis and sensitized with the semiconductor nanoparticles, through a single-source precursor decomposition method. ZnS and Bi2S3 nanoparticles were successfully grown onto the TNF's surface and Bi2S3-ZnS/TNF nanocomposite materials with different layouts were obtained using either a layer-by-layer or a co-sensitization approach. The samples' photocatalytic performance was first evaluated through the production of the hydroxyl radical using terephthalic acid as probe molecule. All the tested samples show photocatalytic ability for the production of this oxidizing species. Afterwards, the samples were investigated for the removal of methylene blue. The nanocomposite materials with best adsorption ability for the organic dye were the ZnS/TNF and Bi2S3ZnS/TNF. The removal of the methylene blue was systematically studied, and the most promising results were obtained considering a sequential combination of an adsorption-photocatalytic degradation process using the Bi2S3ZnS/TNF powder as a highly adsorbent and photocatalyst material.Comment: 26 pages, 10 figure

Background information and biorefinery status, potential and Sustainability: Task 2.1.2 Market and Consumers; Carbohydrates

This report was produced to give an overview of present and future market for biorefinery products based on carbohydrates. Various studies show that there is a wealth of possible molecules and products that can be produced from carbohydrates. Carbohydrates already find significant application in starch products and cellulose plastics and fibres. However, for a biorefinery to operate in an economically sustainable way, applications for (preferably all) biomass ingredients need to be found. Presumably the optimal mix of applications will be a combination of larger volume/smaller value and smaller volume/higher value applications. For this study we therefore have taken a molecular approach. Looking at the size of possible end markets for the molecules that can be based on carbohydrates a number of main products come into view: dialcohols, dioic acids, 2,5 furan dicarboxylic acid and ethanol. These molecules with a wide application range can serve as basis targets for the carbohydrate stream of a biorefinery, provided the production processes are optimised to make them competitive to the petrochemical counterparts. Speciality applications for the resulting side streams will then need to be found on a case by case basis

Effect of hydroxyapatite nanoparticles on the degradability of random poly(butylene terephthalate-co-aliphatic dicarboxylate)s having a high content of terephthalic units

Copolyesters derived from 1,4-butanediol and constituted also of aliphatic and aromatic dicarboxylate units in a molar ratio of 3:7 were synthesized by a two-step polycondensation procedure. Succinic, adipic, and sebacic acids were specifically selected as the aliphatic component whereas terephthalic acid was chosen as the aromatic moiety. The second synthesis step was a thermal transesterification between the corresponding homopolymers, always attaining a random distribution as verified by NMR spectroscopy. Hybrid polymer composites containing 2.5 wt % of hydroxyapatite (HAp) were also prepared by in situ polymerization. Hydroxyl groups on the nanoparticle surface allowed the grafting of polymer chains in such a way that composites were mostly insoluble in the typical solvents of the parent copolyesters. HAp had some influence on crystallization from the melt, thermal stability, and mechanical properties. HAp also improved the biocompatibility of samples due to the presence of Ca2+ cations and the damping effect of phosphate groups. Interestingly, HAp resulted in a significant increase in the hydrophilicity of samples, which considerably affected both enzymatic and hydrolytic degradability. Slight differences were also found in the function of the dicarboxylic component, as the lowest degradation rates was found for the sample constituted of the most hydrophobic sebacic acid units. View Full-TextPeer ReviewedPostprint (published version

Commercial fire-retarded PET formulations - relationship between thermal degradation behaviour and fire-retardant action

Many types of fire-retardants are used in poly(ethylene terephthalate), PET, formulations, and two commercial fire retardants, Ukanol(TM) and Phosgard(TM), have been shown to improve significantly PET flame-retardancy when used as comonomers. Phosgard incorporates a phosphorus atom within the main chain whereas Ukanol incorporates a phosphorus atom as a pendent substituent. Despite their acknowledged effectiveness, the mode of action of these fire retardants remains unclear, and in this paper we present a comparison of the overall thermal degradation behaviour of PET and Ukanol and Phosgard fire retarded formulations. DSC and particularly TGA data show that both Ukanol and Phosgard have some stabilising influence on PET degradation, especially under oxidative conditions. TGA and pyrolysis experiments both clearly indicate that neither additive acts as a char promoter. Only the Phosgard formulation shows any release of volatile phosphorus species which could act in the gas phase. On the other hand, the most striking feature of the pyrolysis experiments is the macroscopic structure of the chars produced by the fire-retarded formulations, which hints at their fire-retardancy action - an open-cell charred foam was obtained upon charring at 400°C or 600°C. This foaming layer between the degrading melt and the flame would lower the amount of fuel available for combustion, and would also limit the feedback of heat to the condensed phase

Pivalolactone, 1 interchange reactions with polypivalolactone

Ester interchange, alcoholysis, and acidolysis of polypivalolactone (PPVL) were studied by melting PPVL with bisphenol diacetates, 1, 4-butanediol, or aromatic diacids. Interchange of PPVL with the diacetates and the diol occured readily, in particular in the presence of a titanium catalyst. Melting PPVL with 10 mol-% of bisphenol-Adiacetate in the presence of 0,5 wt.% tetrabutylorthotitanate resulted in an incorporation of 33% of the diacetate in the polymer chains, whereas the logarithmic viscosity number decreased by 81%. The ester interchange was suggested to proceed by an initial cleavage of ester bonds in the polymer chain of PPVL, resulting in the formation of shorter chains, followed by a reaction between the newly formed ester end-groups and initially present hydroxyl chain ends. The acidolysis of PPVL with the diacids proved to be less effective; in the case of the acidolysis of PPVL with 10 mol-% isophthalic acid, less than 1% of the diacid was incorporated in the polymer chains and a decrease in the logarithmic viscosity number of only 22% was found. Both the high stability of the ester bond in PPVL towards acids in general and the heterogeneity of these systems were supposed to cause the behaviour of PPVL with respect to acidolysis. The results concerning the interchange reactions with PPVL were compared with studies on other polyesters

Copolyamides of nylon-4,6 and nylon-4,T

Copolyamides of nylon-4,6 and nylon-4,T were prepared by a two-step method: (1) a prepolymerization in an autoclave (40 min at 210°C) and (2) a postcondensation in the solid state (4 h, 260°C). On these materials was studied the melting behavior with DSC, the crystalline structure with WAXS, the water absorption, and the mechanical properties with a torsion pendulum. In these copolyamides the order was found to remain high, but the crystalline structures of -4,6 and -4,T were not isomorphous. The torsion moduli increased with -4,T content both at RT and at 140°C

Magnetoelectrically driven catalytic degradation of organics

Here, we report the catalytic degradation of organic compounds by exploiting the magnetoelectric (ME) nature of cobalt ferrite-bismuth ferrite (CFO-BFO) core-shell nanoparticles. The combination of magnetostrictive CFO with the multiferroic BFO gives rise to a magnetoelectric engine that purifies water under wireless magnetic fields via advanced oxidation processes, without involvement of any sacrificial molecules or co-catalysts. Magnetostrictive CoFe2O4 nanoparticles are fabricated using hydrothermal synthesis, followed by sol-gel synthesis to create the multiferroic BiFeO3 shell. We perform theoretical modeling to study the magnetic field induced polarization on the surface of magnetoelectric nanoparticles. The results obtained from these simulations are consistent with the experimental findings of the piezo-force microscopy analysis, where we observe changes in the piezoresponse of the nanoparticles under magnetic fields. Next, we investigate the magnetoelectric effect induced catalytic degradation of organic pollutants under AC magnetic fields and obtained 97% removal efficiency for synthetic dyes and over 85% removal efficiency for routinely used pharmaceuticals. Additionally, we perform trapping experiments to elucidate the mechanism behind the magnetic field induced catalytic degradation of organic pollutants by using scavengers for each of the reactive species. Our results indicate that hydroxyl and superoxide radicals are the main reactive species in the magnetoelectrically induced catalytic degradation of organic compounds

A Strategy for the Design of Flame Retardants: Cross-linking Processes

Cross-linking is identified as an effective means for flame retardation of polymers and schemes for the cross-linking of poly(ethylene terephthalate) and poly(methyl methacrylate) are presented. For poly(ethylene terephthalate) the scheme involves polymerization of the initially produced vinyl ester. This is followed by chain-stripping, producing a polyene, and cyclization of this polyene. For poly(methyl methacrylate) the scheme entails the formation of anhydride linkages between adjacent polymer strands. Evidence is presented to show the efficacy of these processes and information is produced to aid in the identification of new flame retardants