Sulfur containing polymers.: Aromatic polydithiocarbonates and polythiocarbonates: synthesis and thermal properties

New polydithiocarbonates and polythiocarbonates were obtained by interfacial polymerization of bis(4-mercaptophenyl)methane, bis(4-mercaptophenyl)ether and bis(4-mercaptophenyl)sulfide with phosgene, bisphenol A bischloroformate and bisphenol A polycarbonate oligomers (-OH/-O-CO-Cl terminated). Polymerization process was carried out under interfacial conditions using a phase-transfer catalyst, as earlier described for the synthesis of polydithiocarbonates and polythiocarbonates from 2,2-bis(4-mercaptophenyl)propane. The structures of the polymers were examined by IR and NMR spectroscopies; their thermal properties were investigated by thermogravimetric analysis and differential scanning calorimetry. In particular, the effect of the substitution of one or both the ethereal oxygen atoms of the carbonate group by sulfur has been analyzed by comparing the T_g values and the ability to crystallize of the sulfur containing polymers with those of the corresponding polycarbonates.     

Microcellular foams from polyethersulfone and polyphenylsulfone: Preparation and mechanical properties

Polymeric foams having microcellular structures were successfully prepared from some high-performance thermoplastics, specifically polyethersulfone and polyphenylsulfone. A two-stage batch foaming process was used and the resulting materials had average cell sizes in the range 2-13 μm, and cell densities the order of 10¹⁰-10¹¹ cells/cm³. The foam densities (relative to those of the unfoamed polymers) were in the range 0.90-0.35. Average cell sizes increased with foaming temperature and foaming time; on the other hand, cell densities and relative foam densities decreased slightly with foaming temperature but remained almost constant with foaming time. Experimental values of Young’s modulus in compression and the elastic collapse strength were higher than theoretically predicated at high relative densities, but the discrepancies became small at lower densities. In contrast, Young’s moduli in tension were in very good agreement with theory, but the relative strengths were somewhat lower than predicated.     

Polyethylene like polymers. Aliphatic polyesters of dodecanedioic acid: 1. Synthesis and properties

A series of aliphatic polyesters has been synthesized starting from 1,12-dodecanedioic acid and aliphatic diols, bearing from 2 to 12 carbon atoms. These polymers, which were fully characterized in terms of chemical structure, molecular weight and thermal behaviour, were obtained as crystalline materials with melting points ranging from 70 to 90 °C and with a relatively high molecular weight. All the monomers used can be obtained from biomasses, as a consequence these materials can be an interesting alternative to synthetic polymers produced from petrochemical processes based on nonrenewable resources.     

Study of the chemical copolymerization of 2-aminoterephthalic acid and aniline.: Synthesis and copolymer properties

Aniline (ANI) and 2-aminoterephthalic acid (2ATA) copolymers, with different compositions, were prepared by chemical oxidative polymerization varying the feed ratio. The new materials have been characterized by techniques such as XPS, FTIR, Raman spectroscopies and thermal analysis. It has been checked that 2ATA units are included in the polymer backbone. Different properties have been studied as solubility, conductivity, optical absorption, fluorescence and electroactivity. The copolymers are soluble in aqueous alkaline medium and show clear electroactivity in aqueous acid medium.     

New hydrofluoropolyethers: I. Synthesis and reaction pathway evaluation

A novel family of hydrofluoropolyethers (HFPEs) was obtained with 60-80% selectivity by hydrogenation of perfluoropolyether acyl chlorides with Pt/CaF₂. These compounds are characterized by a macromeric fluorinated body end-capped, on one or both sides, by a (1,1-difluoro)ethoxy group. A reaction pathway for the reduction was proposed consistently with the observed yields and side products. The hemiacetal originated by reaction of the aldehyde (first product of reduction) with the corresponding alcohol was postulated to be the key precursor leading to the HFPE. The metal appears to play a fundamental role promoting the hydrogenolysis of this unexpected intermediate. Exhaustive reduction of the alcohol, generally recognized as the path affording hydrocarbons in the hydrogenation of acyl chlorides, was excluded by products analysis and by specific experiments.     

Liquid crystalline polymers: 14. Synthesis and thermal behaviour of some polyethers containing azo-mesogens

The paper presents a study on the relationship between the structure of macromolecular chain and its capacity to generate a mesophase, when mesogens with an azobenzene structure are implied. The polymers have been synthesized by phase transfer catalysis starting from 1,9-dichlorononane and different bisphenols: diphenyl-4,4^′-bis[(azo-4-)phenol], 4,4^′-dihydroxyazobenzene, 4,4^′-dihydroxydiphenyl, bisphenol A and 4,4^′-dihydroxybenzophenone. The polymers have been characterized by ¹H-NMR spectroscopy, DSC calorimetry, optical microscopy in polarized light and thermogravimetrical analysis. Theoretical conformational studies, using molecular simulations have also been performed. Due to their particular geometry, bis-(azobenzene) units are better mesogenic groups as compared with the azobenzene ones. The highly aromatic structure makes impossible the samples isotropisation, as the degradation processes starting advance. For these polymers, under UV irradiation, due to the presence of two azo groups in each mesogen unit, strong conformational modifications are expected. The replacement of the bis-(azobenzene) moieties with azobenzene ones reduces the transition temperatures, making possible the samples isotropisation.