Electrically-Conductive Polyketone Nanocomposites Based on Reduced Graphene Oxide

In this work, we investigated the functionalization of polyketone 30 (PK30) with glycyl-glycine (Gly-Gly) via the Paal-Knorr reaction with the aim of homogenously dispersing two types of reduced graphene oxide (rGO, i.e., lrGO and hrGO, the former characterized by a lower degree of reduction in comparison to the latter) by non-covalent interactions. The functional PK30-Gly-Gly polymer was effective in preparing composites with homogeneously distributed rGO characterized by an effective percolation threshold at 5 wt. %. All the composites showed a typical semiconductive behavior and stable electrical response after several heating/cooling cycles from 30 to 115 °C. Composites made by hrGO displayed the same resistive behaviour even if flanked by a considerable improvement on conductivity, in agreement with the more reduced rGO content. Interestingly, no permanent percolative network was shown by the composite with 4 wt. % of lrGO at temperatures higher than 45 °C. This material can be used as an ON-OFF temperature sensor and could find interesting applications as sensing material in soft robotics applications

pH-Responsive Polyketone/5,10,15,20-Tetrakis-(Sulfonatophenyl)Porphyrin Supramolecular Submicron Colloidal Structures

In this work, we prepared color-changing colloids by using the electrostatic self-assembly approach. The supramolecular structures are composed of a pH-responsive polymeric surfactant and the water-soluble porphyrin 5,10,15,20-tetrakis-(sulfonatophenyl)porphyrin (TPPS). The pH-responsive surfactant polymer was achieved by the chemical modification of an alternating aliphatic polyketone (PK) via the Paal-Knorr reaction with N-(2-hydroxyethyl)ethylenediamine (HEDA). The resulting polymer/dye supramolecular systems form colloids at the submicron level displaying negative zeta potential at neutral and basic pH, and, at acidic pH, flocculation is observed. Remarkably, the colloids showed a gradual color change from green to pinky-red due to the protonation/deprotonation process of TPPS from pH 2 to pH 12, revealing different aggregation behavior

Mechanical properties and electrical surface charges of microfibrillated cellulose/imidazole-modified polyketone composite membranes

In the present work, microfibrillated cellulose (MFC) suspensions were produced by high-pressure homogenization and subsequently used to fabricate MFC membranes (C-1) by vacuum filtration followed by hot-pressing. A polyketone (PK50) was chemically modified by Paal-Knorr reaction to graft imidazole (IM) functional groups along its backbone structure. The resulting polymer is referred to as PK50IM80. By solution impregnation, C-1 was immersed in an aqueous solution of PK50IM80 and subsequently hot pressed, resulting in the fabrication of MFC/PK50IM80 composite membranes (C-IMP). Another method, referred to as solution mixing, consisted in adding MFC into an aqueous solution of PK50IM80 followed by vacuum filtration and hot-pressing to obtain MFC/PK50IM80 composite membranes (C-MEZC). C-IMP and C-MEZC were characterized by a wide range of analytical techniques including, X-ray photoelectron spectroscopy, Fourier-transform infrared chemical imaging, scanning electron microscopy, atomic force microscopy, dynamical mechanical analysis, tensile testing as well as streaming zeta potential, and compared to C-1 (reference material). The results suggested that C-IMP possess a more homogeneous distribution of PK50IM80 at their surface compared to C-MEZC. C-IMP was found to possess significantly enhanced Young's modulus compared to C-1 and C-MEZC. The tensile strength of C-IMP was found to improve significantly compared to C-1, whereas C-1 possessed significantly higher tensile index than C-IMP and C-MEZC. Furthermore, the presence of PK50IM80 at the surface of MFC was found to significantly shift the isoelectric point (IEP) of the membranes from pH 2.3 to a maximum value of 4.5 for C-IMP. Above the IEP, C-IMP and C-MEZC were found to possess significantly less negative electrical surface charges (plateau value of -25 mV at pH 10) when compared to C-1 (plateau value of -42 mV at pH 10). Our approach may have implication to broaden the range of filtration applications of MFC-based membranes

Synthesis of poly(1-vinylimidazole)-block-poly(9-vinylcarbazole) copolymers via RAFT and their use in chemically responsive graphitic composites

This study reports the synthesis of novel poly(1-vinylimidazole)-b-poly(9-vinylcarbazole) (PVI-b-PVK) block copolymers with varying monomer ratios using reversible addition-fragmentation chain-transfer (RAFT) polymerization and their incorporation in responsive composite materials. Specifically, non-covalent exfoliation of two different conductive fillers, multi-walled carbon nanotubes (MWCNTs) or reduced graphene oxide (rGO), was studied. The percolation threshold of the synthesized nanocomposites was dependent on the polymer used for dispersion, showing a better affinity of the fillers for block copolymers with higher relative carbazole content. Resistivity measurements showed selective variation in the resistance signal when the materials were exposed to various organic solvents and acids, providing a good basis for the design of sensing devices

Thermally Switchable Electrically Conductive Thermoset rGO/PK Self-Healing Composites

Among smart materials, self-healing is one of the most studied properties. A self-healing polymer can repair the cracks that occurred in the structure of the material. Polyketones, which are high-performance thermoplastic polymers, are a suitable material for a self-healing mechanism: a furanic pendant moiety can be introduced into the backbone and used as a diene for a temperature reversible Diels-Alder reaction with bismaleimide. The Diels-Alder adduct is formed at around 50 °C and broken at about 120 °C, giving an intrinsic, stimuli-responsive self-healing material triggered by temperature variations. Also, reduced graphene oxide (rGO) is added to the polymer matrix (1.6–7 wt%), giving a reversible OFF-ON electrically conductive polymer network. Remarkably, the electrical conductivity is activated when reaching temperatures higher than 100 °C, thus suggesting applications as electronic switches based on self-healing soft devices

Electroactive performance and cost evaluation of carbon nanotubes and carbon black as conductive fillers in self-healing shape memory polymers and other composites

Multiwalled carbon nanotubes (MWCNT) and carbon black (CB) have been widely used as conductive fillers in electroactive polymer composites. MWCNT-based composites generally have lower resistivity and percolation thresholds, while CB-based ones are considerably cheaper. To balance these pros and cons, ternary composites (TCs) (polymer-MWCNT-CB) can be formulated. Here, we prepared electroactive MWCNT-CB TCs capable of self-healing and with shape memory properties, based on polyketones reversibly-crosslinked via Diels-Alder chemistry. Unexpectedly, the cheaper CB-rich formulations had lower resistivities, thus better electroactive self-healing and shape memory responses. Nonetheless, not all electroactive MWCNT-CB TCs have this clear cost-effectiveness. We evaluated the cost-performance of multiple reported MWCNT-CB TCs systems and found different general trends (positive, negative, and synergistic cost-efficiency relationships). Thus, the cost-effectiveness of these fillers (and their combination) greatly depends on each composite system and what it is intended for. This work includes the first systematic report on cost-performance of MWCNT and CB as conductive fillers

Functionalized aliphatic polyketones with germicide activity

The COVID-19 pandemic has further confirmed to the community that direct contact with contaminated surfaces and objects represents an important source of pathogen spreading among humans. Therefore, it is of paramount importance to design effective germicidal paints to ensure a rapid and potent disinfectant action of surfaces. In this work, we design novel germicide polymeric coatings by inserting quaternary ammonium and sugar groups on the macromolecular backbone, thus respectively endowing the polymer with germicide features and hydrophilicity to interact with the surfaces. An aliphatic polyketone was selected as a starting polymer matrix that was functionalized with primary amine derivatives via the Paal–Knorr reaction. The resulting polymers were deposited on cellulose filter papers and checkboard charts with excellent coating yield and substrate coverage as determined by scanning electron microscopy for cellulose. Remarkably, the substrates coated by the functional polymers bearing quaternary ammonium compounds showed excellent bactericide properties with antibacterial rate of 99% and logarithmic reduction of >3. Notably, the polymers with higher hydrophobicity showed better retention on the substrate after being treated with water at neutral pH

Polymeric surfactants based on the chemical modification of alternating aliphatic polyketones

Abstract: Polymeric surfactants are macromolecules (polymers) with hydrophobic and hydrophilic segments distributed all over the polymer backbone. Due to their amphiphilic attributes, they have been used in pharmacology, oil recovery, micellar catalysis, among others. Polymeric surfactants are synthesized by different methods. One of them is the chemical modification of preformed polymers. In this thesis, we focused on the chemical modification of alternating polyketones for the preparation of pH-responsive polymeric surfactants, which can bear different functional groups such as aliphatic amines and charge aromatic groups. In addition, the Paal-Knorr reaction (the synthetic approach used through this thesis) allowed the precise tuning of the polymer hydrophobic/hydrophilic properties. The most interesting applications of these polymeric surfactants were the encapsulation of hydrophobic antibiotics, formation of functional supramolecular structures with porphyrins, and the preparation of redox-active organic nanoparticles

Nitrogen Dioxide Optical Sensor Based on Redox‐Active Tetrazolium/Pluronic Nanoparticles Embedded in PDMS Membranes

Anthropogenic toxic vapour and gases are a worldwide threat for human health and to the environment. Therefore, it is crucial to develop highly sensitive devices that guarantee their rapid detection. Here, we prepared redox‐switchable colloids by the in‐situ reduction of 2,3,5‐tri-phenyl‐2H‐tetrazolium (TTC) into triphenyl formazan (TF) stabilised with Pluronic F127 in aqueous media. The colloids were readily embedded in polydimethylsiloxane (PDMS) to produce a selective colour‐switchable membrane for nitrogen dioxide (NO2) detection. We found that the TTC reduction resulted in the production of red‐coloured colloids with zeta potential between −1 to 3 mV and hydrodynamic diameters between 114 to 305 nm as hydrophobic dispersion in aqueous media stabilised by Pluronic at different molar concentrations. Moreover, the embedded colloids rendered highly homogenous red colour gas‐permeable PDMS elastomeric membrane. Once exposed to NO2, the membrane began to bleach after 30 s due to the oxidation of the embedded TF and undergo a complete decolouration after 180 s. Such features allowed the membrane integration in a low‐cost sensing device that showed a high sensitivity and low detection limit to NO2

Polyketone-Based Anion-Exchange Membranes for Alkaline Water Electrolysis

Anion-exchange membranes (AEMs) are involved in a wide range of applications, including fuel cells and water electrolysis. A straightforward method for the preparation of efficient AEMs consists of polymer functionalization with robust anion-exchange sites. In this work, an aliphatic polyketone was functionalized with 1-(3-aminopropyl)imidazole through the Paal–Knorr reaction, with a carbonyl (CCO %) conversion of 33%. The anion-exchange groups were generated by the imidazole quaternization by using two different types of alkyl halides, i.e., 1,4-iodobutane and 1-iodobutane, with the aim of modulating the degree of crosslinking of the derived membrane. All of the membranes were amorphous (Tg ∼ 30 °C), thermally resistant up to 130 °C, and had a minimum Young’s modulus of 372 ± 30 MPa and a maximum of 86 ± 5 % for the elongation at break for the least-crosslinked system. The ionic conductivity of the AEMs was determined at 25 °C by electrochemical impedance spectroscopy (EIS), with a maximum of 9.69 mS/cm, i.e., comparable with that of 9.66 mS/cm measured using a commercially available AEM (Fumasep-PK-130). Future efforts will be directed toward increasing the robustness of these PK-based AEMs to meet all the requirements needed for their application in electrolytic cells