Synthesis of Soluble High Molar Mass Poly(Phenylene Methylene)-Based Polymers.

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 Mn 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.

Improving the Corrosion Protection of Poly(phenylene methylene) Coatings by Side Chain Engineering: The Case of Methoxy-Substituted Copolymers.

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.

Smart Anticorrosion Coatings Based on Poly(phenylene methylene): An Assessment of the Intrinsic Self-Healing Behavior of the Copolymer.

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).