Evidence through Thermal Analysis of Retro Diels-Alder Reaction in Model Networks Based on Anthracene Modified Polyester Resins.

The present work is focused on polyester resins obtained from the diglycidyl ether of bisphenol A and anthracene modified 5-maleimidoisophthalic acid. Because the maleimide-anthracene Diels-Alder (DA) adduct is stable at high temperatures, it is considered a good option for high performance polymers. However, the information related to the retroDA reaction for this type of adduct is sometimes incoherent. A detailed thermal study (conventional TGA, HiRes TGA, MTGA, DSC, MDSC) was performed in order to establish whether the rDA reaction can be revealed for this type of anthracene modified polyester resins. The TGA method confirmed the cleavage of the anthracene-maleimide DA adduct, while the DSC demonstrated the presence of anthracene in the system. At high temperatures, unprotected maleimide homopolymerizes and/or reacts with allyl groups according to the -ene reaction. Therefore, the thermal DA reaction is not displayed anymore upon the subsequent cooling, and the glass transition region is registered at a higher temperature range during the second heating. The use of sample-controlled thermal analysis (HiRes TGA) and MTGA improved the TGA result; however, it was not possible to separate the very complex degradation processes that are interconnected.

Novel Bio-Based Materials: From Castor Oil to Epoxy Resins for Engineering Applications.

The paper presents the synthesis and thermal behavior of novel epoxy resins prepared from epoxidized castor oil in the presence of or without trimethylolpropane triglycidyl ether (TMP) crosslinked with 3-hexahydro-4-methylphtalic anhydride (MHHPA) and their comparison with a petroleum-based epoxy resin (MHHPA and TMP). Epoxidized castor oil (ECO) was obtained via in situ epoxidation of castor oil with peroxyacetic acid. The chemical structures of castor oil (CO), ECO, and epoxy matrix were confirmed using FT-IR and 1H-NMR spectroscopy. The morphological and thermal behavior of the resulting products have been investigated. Compared to petroleum-based resins, castor oil-based ones have a lower Tg. Anyway, the introduction of TMP increases the Tg of the resins containing ECO. The morphological behavior is not significantly influenced by using ECO or by adding TMP in the synthesis of resins. The dielectric properties of epoxy resins have been analyzed as a function of frequency (1 kHz-1 MHz) and temperature (-50 to 200 °C). The water absorption test showed that as Tg increased, the percent mass of water ingress decreased.

MWCNTs Composites-Based on New Chemically Modified Polysulfone Matrix for Biomedical Applications.

Polyvinyl alcohol (PVA) is a non-toxic biosynthetic polymer. Due to the hydrophilic properties of the PVA, its utilization is an easy tool to modify the properties of materials inducing increased hydrophilicity, which can be noticed in the surface properties of the materials, such as wettability. Based on this motivation, we proposed to obtain high-performance composite materials by a facile synthetic method that involves the cross-linking process of polyvinyl alcohol (PVA) with and aldehyde-functionalized polysulfone(mPSF) precursor, prior to incorporation of modified MWCNTs with hydrophilic groups, thus ensuring a high compatibility between the polymeric and the filler components. Materials prepared in this way have been compared with those based on polyvinyl alcohol and same fillers (mMWCNTs) in order to establish the influence of the polymeric matrix on the composites properties. The amount of mMWCNTs varied in both polymeric matrices between 0.5 and 5 wt%. Fourier transformed infrared with attenuated total reflectance spectroscopy (FTIR-ATR) was employed to confirm the changes noted in the PVA, mPSF and their composites. Hemolysis degree was investigated in correlation with the material structural features. Homogenous distribution of mMWCNTs in all the composite materials has been confirmed by scanning electron microscopy. The hydrophilicity of both composite systems, estimated by the contact angle method, was influenced by the presence of the filler amount mMWCNTs in both matrices (PVA and mPSF). Our work demonstrates that mPSF/mMWCNTs and PVA/mMWCNTs composite could be used as water purification or blood-filtration materials.

Fluorescence Modulation and Photochromism in Azobismaleimide Derivatives.

A fluorophore-photochrome system incorporating an aryleneimine type fluorophore and an azobismaleimide photochrome was developed and the photochemical properties of this system were investigated. The photoisomerization of trans-azoaromatic chromophore leads to the increase of the fluorescence intensity of fluorophore. The cis azobismaleimide isomers revert photochemically to the trans form and the emission intensity decreases. The fluorescence intensity of the imine fluorophore can be modulated under irradiation with UV and visible (436 nm) light due to reversible trans-cis-trans photoisomerization of azobismaleimide partner. The photoisomerization kinetics was obeyed a first-order relationship with a rate constant of 1.95 × 10(-2) s(-1) for azobismaleimide/imine fluorophore system and for polyazothioetherimide/imine derivative the kinetics was described by a biexponential equation.

Optical properties of some new azo photoisomerizable bismaleimide derivatives.

Novel polythioetherimides bearing azobenzene moieties were synthesized from azobismaleimides and bis-2-mercaptoethylether. Kinetics of trans-cis photoisomerization and of thermal conversion of cis to trans isomeric forms were investigated in both polymer solution and poly(methyl methacrylate) doped films using electronic absorption spectroscopy. Thermal recovery kinetics is well described by a two-exponential relation both in solution and polymer matrix, while that of low molecular weight azobismaleimide fit a first-order equation. The photoinduced cis-trans isomerization by visible light of azobenzene chromophores was examined in solution and in polymer films. The rate of photoinduced recovery was very high for azobismaleimides.