Search Results (8)

Poly(phenylene methylene) (PPM) is a multifunctional polymer that is also active as an anticorrosion fluorescent coating material. Although this polymer was synthesized already more than 100 years ago, a versatile synthetic route to obtain soluble high molar mass polymers based on PPM has yet to be achieved. In this article, the influence of bifunctional bis-chloromethyl durene (BCMD) as a branching agent in the synthesis of PPM is reported. The progress of the reaction was followed by gel permeation chromatography (GPC) and NMR analysis. PPM-based copolymers with the highest molar mass reported so far for this class of materials (up to M_n of 205,300 g mol⁻¹) were isolated. The versatile approach of using BCMD was confirmed by employing different catalysts. Interestingly, thermal and optical characterization established that the branching process does not affect the thermoplastic behavior and the fluorescence of the material, thus opening up PPM-based compounds with high molar mass for applications. Full article

The sustainable development of innovative eco-friendly multifunctional nanocomposites, possessing superior characteristics, is a noteworthy topic. Novel semi-interpenetrated nanocomposite films based on poly(vinyl alcohol) covalently and thermally crosslinked with oxalic acid (OA), reinforced with a novel organophosphorus flame retardant (PFR-4) derived from co-polycondensation in solution reaction of equimolar amounts of co-monomers, namely, bis((6-oxido-6H-dibenz[c,e][1,2]oxaphosphorinyl)-(4-hydroxyaniline)-methylene)-1,4-phenylene, bisphenol S, and phenylphosphonic dichloride, in a molar ratio of 1:1:2, and additionally doped with silver-loaded zeolite L nanoparticles (ze-Ag), have been prepared by casting from solution technique. The morphology of the as prepared PVA-oxalic acid films and their semi-interpenetrated nanocomposites with PFR-4 and ze-Ag was investigated by scanning electron microscopy (SEM), while the homogeneous distribution of the organophosphorus compound and nanoparticles within the nanocomposite films has been introspected by means of energy dispersive X-ray spectroscopy (EDX). It was established that composites with a very low phosphorus content had noticeably improved flame retardancy. The peak of the heat release rate was reduced up to 55%, depending on the content of the flame-retardant additive and the doping ze-Ag nanoparticles introduced into the PVA/OA matrix. The ultimate tensile strength and elastic modulus increased significantly in the reinforced nanocomposites. Considerably increased antimicrobial activity was revealed in the case of the samples containing silver-loaded zeolite L nanoparticles. Full article

This work aims to improve the corrosion protection features of poly(phenylene methylene) (PPM) by sidechain engineering inserting methoxy units along the polymer backbone. The influence of side methoxy groups at different concentrations (4.6% mol/mol and 9% mol/mol) on the final polymer properties was investigated by structural and thermal characterization of the resulting copolymers: co-PPM 4.6% and co-PPM 9%, respectively. Then, coatings were processed by hot pressing the polymers powder on aluminum alloy AA2024 and corrosion protection properties were evaluated exposing samples to a 3.5% w/v NaCl aqueous solution. Anodic polarization tests evidenced the enhanced corrosion protection ability (i.e., lower current density) by increasing the percentage of the co-monomer. Coatings made with co-PPM 9% showed the best protection performance with respect to both PPM blend and PPM co-polymers reported so far. Electrochemical response of aluminum alloy coated with co-PPM 9% was monitored over time under two “artificially-aged” conditions, that are: (i) a pristine coating subjected to potentiostatic anodic polarization cycles, and (ii) an artificially damaged coating at resting condition. The first scenario points to accelerating the corrosion process, the second one models damage of the coating potentially occurring either due to natural deterioration or due to any accidental scratching of the polymer layer. In both cases, an intrinsic self-healing phenomenon was indirectly argued by the time evolution of the impedance and of the current density of the coated systems. The degree of restoring to the “factory conditions” by co-polymer coatings after self-healing events is eventually discussed. Full article

Complexes of poly(phenylene methylene) (PPM) with silver(I) ions and tricarbonylchromium(0) moieties, respectively, were synthesized. ¹³C NMR spectra indicate interaction of phenylene groups with silver(I) and chromium(0), and peak broadening implies dynamic behavior of the silver(I) complexes, with all phenylene groups temporarily involved in coordination, in contrast to the chromium complexes. About 5–10% of the phenylene groups are coordinated to metal atoms. ¹H NMR and IR spectra, in the case of chromium(0), and the solubility of silver salts in the presence of PPM provide further evidence of coordination. The complexes are soluble in chloroform, but the silver complexes decay in tetrahydrofuran (second-order kinetics were observed in an example). The photoluminescence (fluorescence) of PPM is maintained upon complexation, although coordination of silver(I) seems to favor the so-called blue phase of PPM relative to the green phase by a factor of approximately two in PL spectra. The pronounced absorption of the tricarbonylchromium(0) units interferes with the blue phase, which almost disappears at a concentration of 50 mg/mL in PLE spectra, whereas the emission maximum of the green phase is hardly affected. This leads to a confinement of the emitted wavelength range of PPM. Thus, the perceived optical emission of PPM can be modified by coordinated entities. Full article

Poly(phenylene methylene) (PPM) is a multifunctional polymer featuring hydrophobicity, high thermal stability, fluorescence and thermoplastic processability. Accordingly, smart corrosion resistant PPM-based coatings (blend and copolymer) were prepared and applied by hot pressing on aluminum alloy AA2024. The corrosion protection properties of the coatings and their dependence on coating thickness were evaluated for both strategies employed. The accelerated cyclic electrochemical technique (ACET), based on a combination of electrochemical impedance spectroscopy (EIS), cathodic polarizations and relaxation steps, was used as the main investigating technique. At the coating thickness of about 50 µm, both blend and copolymer PPM showed effective corrosion protection, as reflected by |Z|_0.01Hz of about 10⁸ Ω cm² over all the ACET cycles. In contrast, when the coating thickness was reduced to 30 µm, PPM copolymer showed neatly better corrosion resistance than blended PPM, maintaining |Z|_0.01Hz above 10⁸ Ω cm² with respect to values below 10⁶ Ω cm² of the latter. Furthermore, the analysis of many electrochemical key features, in combination with the optical investigation of the coating surface under 254 nm UV light, confirms the intrinsic self-healing ability of the coatings made by PPM copolymer, contrary to the reference specimen (i.e., blend PPM). Full article

Poly(phenylene methylene) (PPM) is a thermally stable, hydrophobic, fluorescent hydrocarbon polymer. Recently, blended PPM has been proposed as a valuable anti-corrosion coating material, and, in particular, rheological additives such as external plasticizers resulted crucial to prevent crack formation. Accordingly, to avoid common problems related to the use of external plasticizers, the development of PPM-related copolymer-based coatings containing n-octyloxy side chains and their anti-corrosion behavior were explored in this study. The aluminum alloy AA2024, widely employed for corrosion studies, was selected as a substrate, covered with a thin layer of a polybenzylsiloxane in order to improve adhesion between the underlying hydrophilic substrate and the top hydrophobic coating. Gratifyingly, coatings with those copolymers were free of bubbles and cracks. The n-octyloxy side-chains may be regarded to adopt the role of a bound plasticizer, as the glass transition temperature of the copolymers decreases with increasing content of alkoxy side-chains. Electrochemical corrosion tests on PPM-substituted coatings exhibited good corrosion protection of the metal surface towards a naturally aerated near-neutrally 3.5% wt.% NaCl neutral solution, providing comparable results to blended PPM formulations, previously reported. Hence, the application of rheological additives can be avoided by use of proper design copolymers. Full article

Poly(phenylene methylene) (PPM) is a thermally stable, hydrophobic, fluorescent hydrocarbon polymer. PPM has been proposed earlier to be useful as a coating material but this polymer was isolated in relevant molar masses only recently, and in large quantities. Accordingly, the preparation of coatings based on PPM and their behavior was explored in this study, with the example of the metal alloy AA2024 as a common substrate for corrosion tests. Coatings free of bubbles and cracks were obtained by hot pressing and application of the following steps: Coating on AA2024 with a layer of polybenzylsiloxane to improve the adhesion between PPM and the metal surface, the addition of polybenzylsiloxane to PPM in order to enhance the viscosity of the molten PPM, and the addition of benzyl butyl phthalate as a plasticizer. Electrochemical corrosion tests showed good protection of the metal surface towards a NaCl solution, thanks to a passive-like behavior in a wide potential window and a very low current density. Remarkably, the PPM coating also exhibited self-healing towards localized attacks, which inhibits the propagation of corrosion. Full article

Poly(phenylene methylene)s (PPMs) with high molar masses were isolated by polymerization of benzyl chloride catalyzed with tungsten(II) compounds and subsequent fractionation. Four different tungsten(II) catalysts were successfully exploited for the polymerization, for which a strict temperature profile was developed. The PPMs possessed roughly a trimodal molar mass distribution. Simple fractionation by phase separation of 2-butanone solutions allowed to effectively segregate the products primarily into PPM of low molar mass (M_n = 1600 g mol⁻¹) and high molar mass (M_n = 167,900 g mol⁻¹); the latter can be obtained in large quantities up to 50 g. The evolution of the trimodal distribution and the monomer conversion was monitored by gel permeation chromatography (GPC) and ¹H NMR spectroscopy, respectively, over the course of the polymerization. The results revealed that polymerization proceeded via a chain-growth mechanism. This study illustrates a new approach to synthesize PPM with hitherto unknown high molar masses which opens the possibility to explore new applications, e.g., for temperature-resistant coatings, fluorescent coatings, barrier materials or optical materials. Full article