Synthesis and characterization of flame retardant unsaturated polyester-allyloxysilane resin for wood coatings.

Fireproof coatings are the simplest, most efficient, and oldest method for protecting a wide range of flammable products, such as wood. Furthermore, surface ignition is the initial phase, so surface protection is essential to reduce fire propagation. Furthermore, delaying the spread of flames can help to save someone when a fire starts. This project synthesized flame-resistant resin starting from tetraallyloxysilane monomer as a halogen-free monomer, an intrinsic flame retardant co-curing agent. The following step synthesized polyester resin using terephthalic acid as a heat-resistant resin. Unsaturated polyester was used by bulk radical polymerization. FT-IR and 1H-NMR analysis showed the successful synthesis of the desired monomer and polymeric compound. The thermal degradation and flame retardancy of pure unsaturated polyester resin (UPE) and allyloxysilane-unsaturated polyester (AUPE) were investigated by thermogravimetric analysis (TGA/DTG/DSC). The burning test and the thermal stability of the coating layers were evaluated using standard UL 94. Physical properties of resins were evaluated using Heat Deflection Temp tests (HDT) ISO 75-A, ASTM 648, Hardness ASTM D2583, Volumetric shrinkage ASTM 3521, and Water absorption ASTM D570. The results of the tests show the successful synthesis and their flame retardant properties.

Macromolecular Dyes by Chromophore-Initiated Ring Opening Polymerization of L-Lactide.

End functionalized polylactides are prepared by ring opening polymerization of L-lactide in the presence of stannous octoate (Sn(Oct)2). Three chromophores, 9H-carbazol-ethanol (CA), 9-fluorenyl-methanol (FM), and 2-(4-(2-chloro-4-nitrophenylazo)-N-ethylphenylamino)ethanol (Disperse Red 13, DR), are for the first time used as co-initiators in the polymerization process. The polymerization reaction is initiated by conventional thermal treatment, but in the case of FM, microwave-assisted polymerization is also carried out. CA and FM absorb and emit in the UV portion of the electromagnetic spectrum, whereas DR absorbs in the visible part. The obtained end-capped polylactides derivatives show the same photophysical properties as the initiator, so they are "macromolecular dyes" (MDs) that can be used "as synthesized" or can be blended with commercial poly(lactic acid) (PLA). The blends of PLA with MDs have ultraviolet-visible (UV-Vis) absorption and fluorescence emission features similar to that of MDs and thermal properties typical of PLA. Finally, migration tests, carried out onto the blends of PLA with MDs and PLA with free chromophores, show that MDs are less released than free chromophores both in solution and in the solid phase.

Characterization of bio-oil and bio-char produced by low-temperature microwave-assisted pyrolysis of olive pruning residue using various absorbers.

Olive pruning residue is largely formed during cultivation, and is usually disposed through open-air combustion directly in the field, but this habit is a possible source of pollution. The pyrolytic conversion of olive pruning residue has been run in a new and very appealing way using microwave as a heating source and different microwave absorbers in a multimode batch reactor. In this way, olive residue is converted into interesting bio-chemical products with a short pyrolysis time, ranging from 15 to 36 min, and with a peak temperature ranging from 450 K to 705 K according to the different microwave absorber. Thus, a very efficient and selective system was realized, which was able to address the process towards the formation of a large amount of bio-char (up to 61.2%) or a high formation of bio-oil (56.2%) and gas (41.7%) with a very low formation of bio-char (2.1%). However, when carbon and iron were used as microwave absorbers, it was possible to obtain an intermediate amount of bio-char (26-30%) and bio-oil (40 wt%). Bio-oils were collected as dark-brown liquids with low viscosity and density. A bio-oil with a low water concentration was obtained using carbon or iron as the microwave absorber. The bio-oils formed in all experiments contained a very large amount of acetic acid, even when NaOH was the microwave absorber. Furthermore, a large amount of aromatics were present in the bio-oil obtained using carbon as the microwave absorber.

Microwave assisted pyrolysis of halogenated plastics recovered from waste computers.

Microwave Assisted Pyrolysis (MAP) of the plastic fraction of Waste from Electric and Electronic Equipment (WEEE) from end-life computers was run with different absorbers and set-ups in a multimode batch reactor. A large amount of various different liquid fractions (up to 76.6wt%) were formed together with a remarkable reduction of the solid residue (up to 14.2wt%). The liquid fractions were characterized using the following different techniques: FT-IR ATR, 1H NMR and a quantitative GC-MS analysis. The liquid fractions showed low density and viscosity, together with a high concentration of useful chemicals such as styrene (up to 117.7mg/mL), xylenes (up to 25.6mg/mL for p-xylene) whereas halogenated compounds were absent or present in a very low amounts.

Protocol: A simple protocol for quantitative analysis of bio-oils through gas- chromatography/mass spectrometry.

A new and simple protocol for quantitative analysis of bio-oils using gas-chromatography/mass spectrometry is suggested. Compounds were identified via their mass spectra, and then unavailable response factors were calculated with respect to diphenyl as the internal standard using a modified method previously suggested for gas chromatography with flame ionization detection. This new protocol was applied to the characterization of bio-oils obtained from the pyrolysis of woods of different sources or using different pyrolysis procedures. This protocol allowed evaluation of the yields of products from poplar pyrolysis (among 50% and 99%), while a reduced amounts of products were identified from the pyrolysis of cellulose (between 46% and 58%). The main product was always acetic acid, but it was formed in very large yields from poplar while lower yields were obtained from cellulose.

Design and solid phase synthesis of new DOTA conjugated (+)-biotin dimers planned to develop molecular weight-tuned avidin oligomers.

Chemical modifications of the biotin carrier in pretargeted avidin­biotin radionuclide therapy may be of paramount importance for tuning the amount of the radioactivity delivered to cancer cells by labelled biotins. We report here the synthesis of a collection of new synthetic DOTA-constructs bearing two (+)-biotin molecules (bis-biotins), designed for the creation of multimeric Av units (tetramers) bonded to the antibody. All the syntheses were carried out following the solid phase strategy and growing the molecules on a Rink Amide resin. The biotin heads are connected through spacers containing PEG or non-PEG residues. Molecular modelling calculations suggested that the Av cross-linking ability of the bis-biotins depends mainly on the spacers length, with the best results being expected for arms affording distances in the range of 10­25 Å between the biotin carboxylate atoms, in the fully extended conformation. SEC-HPLC MALLS analysis of the products of our Av/bis-biotin reaction mixtures have confirmed this hypothesis. The bis-biotin 16, where the non-PEG linker ensured a distance of 26.7 Å between the biotin moieties, gave about 50% of Av oligomers while the shorter analogue 18 (19.5 Å) afforded 100% of an Av polymer containing about 21 protein units. Remarkably, the solubility of both the bis-biotins, i.e.16 and 18, in aqueous solutions was good and they showed excellent stability against the action of peptidases.

A comprehensive mechanism of fibrin network formation involving early branching and delayed single- to double-strand transition from coupled time-resolved X-ray/light-scattering detection.

The formation of a fibrin network following fibrinogen enzymatic activation is the central event in blood coagulation and has important biomedical and biotechnological implications. A non-covalent polymerization reaction between macromolecular monomers, it consists basically of two complementary processes: elongation/branching generates an interconnected 3D scaffold of relatively thin fibrils, and cooperative lateral aggregation thickens them more than 10-fold. We have studied the early stages up to the gel point by fast fibrinogen:enzyme mixing experiments using simultaneous small-angle X-ray scattering and wide-angle, multi-angle light scattering detection. The coupled evolutions of the average molecular weight, size, and cross section of the solutes during the fibrils growth phase were thus recovered. They reveal that extended structures, thinner than those predicted by the classic half-staggered, double-stranded mechanism, must quickly form. Following extensive modeling, an initial phase is proposed in which single-bonded "Y-ladder" polymers rapidly elongate before undergoing a delayed transition to the double-stranded fibrils. Consistent with the data, this alternative mechanism can intrinsically generate frequent, random branching points in each growing fibril. The model predicts that, as a consequence, some branches in these expanding "lumps" eventually interconnect, forming the pervasive 3D network. While still growing, other branches will then undergo a Ca(2+)/length-dependent cooperative collapse on the resulting network scaffolding filaments, explaining their sudden thickening, low final density, and basic mechanical properties.

Ultrasounds in melted poly(ethylene glycol) promote copper-catalyzed cyanation of aryl halides with K(4)[Fe(CN)(6)].

Melted poly(ethylene glycols) (PEGs) were used for the first time as solvent for the sonochemically promoted cyanation of aryl halides employing inexpensive and safe K4[Fe(CN)6] and a relatively low amount of Cu-based catalyst. The Mw (weight-average polymer molecular weight) of PEG proved to notably influence the substrate conversion, which is indicative of a strong dependence of the sonication efficacy on solvent properties. Gel permeation chromatography (GPC), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) contributed to the characterization of the polymer and the elucidation of the catalytic system.

High-pressure reactivity of L,L-lactide.

L,L-Lactide, a dimer of L-lactic acid, is the typical monomer used for the catalytic synthesis of poly(L-lactic acid) (PLLA). We studied its phase diagram and reactivity at high pressure and high temperature by means of a diamond anvil cell. FTIR and Raman spectroscopy were employed to probe the changes occurring in the sample. An increase of temperature at pressure higher than 0.1 GPa revealed a solid-solid phase transition before the melting. A reaction was observed immediately after the melting with the almost complete transformation of the starting reactant to an amorphous poly(lactic acid) (PLA). The increase of pressure was found to accelerate the process, suggesting the reaction rate to be limited in the diffusion step. A steeper acceleration, likely due to multiphoton absorption processes of the 647.1 nm laser light by PLA, was observed in the Raman experiments.

A convenient route to the synthesis of isotopomeric dihydro-2(3H)furanones.

A general synthetic procedure leading to isotopomeric dihydro-2(3H)furanones (gamma-butyrolactones) containing two, four, or six deuterium atoms has been developed. The labeled dihydro-2(3H)furanones were synthesized in quantitative yield from the saturated diacid C4 (succinic) or unsaturated diacids C4 (fumaric, maleic, or acetylendicarboxylic) in the presence of Ru4H4(CO)8(PBu3)4 using a deuterium pressure of 180 bar at 180 degrees C. This methodology was applied to the total synthesis of a hexadeuterated matairesinol lignan: The 3,4-bis[[3-methoxy-4-(phenylmethoxy)phenyl]methyl]dihydro-2(3H)furanone-[7,7',8,8',9',9'-D6] (benzyl-protected matairesinol-D6) was fully characterized.