Thermally reversible thermoset materials based on the chemical modification of alternating aliphatic polyketones

This thesis focused on the synthesis and characterization of different kinds of reversible thermosets and thermoset nanocomposite materials by using alternating aliphatic polyketone (PK) as raw material. Fundamental knowledge was generated regarding the molecular design of new polymers via chemical modification of PK with aliphatic and aromatic amine compounds. The resulting thermally reversible thermoset systems were investigated to outline the benefits for the synergistic cooperation between reversible covalent and supramolecular interactions. Moreover, improvements regarding the mechanical performance, reversibility, recyclability, self-healing and electrical conductivity of the thermosets were investigated by incorporating rubber particles and nanofillers into the thermoset matrices. In first instance we investigated the chemical modification of alternating aliphatic polyketones with aliphatic and aromatic amine compounds using the Paal-Knorr reaction to obtain thermally reversible polymers with relatively high glass transition temperatures. These materials display the desired mechanical properties with the exception of toughness. This could be achieved by preparing a reversible and toughened thermoset system based on the covalent incorporation of furan-functionalized ethylene-propylene rubber into a thermoset furan-functionalized polyketone. In order to confer also electrical properties to these materials, conductive nanocomposites containing well-distributed, exfoliated and undamaged MWCNTs were prepared. These new materials, designed by mixing furan-functionalized polyketone cross-linked with aromatic bis-maleimide and MWCNTs via Diels-Alder (DA) reversible cycloaddition, display electrically-induced self-healing properties

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

Effect of the polyketone aromatic pendent groups on the electrical conductivity of the derived MWCNTs-based nanocomposites

Electrically conductive plastics with a stable electric response within a wide temperature range are promising substitutes of conventional inorganic conductive materials. This study examines the preparation of thermoplastic polyketones (PK30) functionalized by the Paal-Knorr process with phenyl (PEA), thiophene (TMA), and pyrene (PMA) pendent groups with the aim of optimizing the non-covalent functionalization of multiwalled carbon nanotubes (MWCNTs) through π-π interactions. Among all the aromatic functionalities grafted to the PK30 backbone, the extended aromatic nuclei of PMA were found to be particularly effective in preparing well exfoliated and undamaged MWCNTs dispersions with a well-defined conductive percolative network above the 2 wt % of loading and in freshly prepared nanocomposites as well. The efficient and superior π-π interactions between PK30PMA and MWCNTs consistently supported the formation of nanocomposites with a highly stable electrical response after thermal solicitations such as temperature annealing at the softening point, IR radiation exposure, as well as several heating/cooling cycles from room temperature to 75 °C

Self-Healing Polymer Nanocomposite Materials by Joule Effect

Nowadays, the self-healing approach in materials science mainly relies on functionalized polymers used as matrices in nanocomposites. Through different physicochemical pathways and stimuli, these materials can undergo self-repairing mechanisms that represent a great advantage to prolonging materials service-life, thus avoiding early disposal. Particularly, the use of the Joule effect as an external stimulus for self-healing in conductive nanocomposites is under-reported in the literature. However, it is of particular importance because it incorporates nanofillers with tunable features thus producing multifunctional materials. The aim of this review is the comprehensive analysis of conductive polymer nanocomposites presenting reversible dynamic bonds and their energetical activation to perform self-healing through the Joule effect

Electrically Self-Healing Thermoset MWCNTs Composites Based on Diels-Alder and Hydrogen Bonds

In this work, we prepared electrically conductive self-healing nanocomposites. The material consists of multi-walled carbon nanotubes (MWCNT) that are dispersed into thermally reversible crosslinked polyketones. The reversible nature is based on both covalent (Diels-Alder) and non-covalent (hydrogen bonding) interactions. The design allowed for us to tune the thermomechanical properties of the system by changing the fractions of filler, and diene-dienophile and hydroxyl groups. The nanocomposites show up to 1 x 10(4) S/m electrical conductivity, reaching temperatures between 120 and 150 degrees C under 20-50 V. The self-healing effect, induced by electricity was qualitatively demonstrated as microcracks were repaired. As pointed out by electron microscopy, samples that were already healed by electricity showed a better dispersion of MWCNT within the polymer. These features point toward prolonging the service life of polymer nanocomposites, improving the product performance, making it effectively stronger and more reliable

Thermoreversibly Cross-Linked EPM Rubber Nanocomposites with Carbon Nanotubes

Conductive rubber nanocomposites were prepared by dispersing conductive nanotubes (CNT) in thermoreversibly cross-linked ethylene propylene rubbers grafted with furan groups (EPM-g-furan) rubbers. Their features were studied with a strong focus on conductive and mechanical properties relevant for strain-sensor applications. The Diels-Alder chemistry used for thermoreversible cross-linking allows for the preparation of fully recyclable, homogeneous, and conductive nanocomposites. CNT modified with compatible furan groups provided nanocomposites with a relatively large tensile strength and small elongation at break. High and low sensitivity deformation experiments of nanocomposites with 5 wt % CNT (at the percolation threshold) displayed an initially linear sensitivity to deformation. Notably, only fresh samples displayed a linear response of their electrical resistivity to deformations as the resistance variation collapsed already after one cycle of elongation. Notwithstanding this mediocre performance as a strain sensor, the advantages of using thermoreversible chemistry in a conductive rubber nanocomposite were highlighted by demonstrating crack-healing by welding due to the joule effect on the surface and the bulk of the material. This will open up new technological opportunities for the design of novel strain-sensors based on recyclable rubbers

Electrically-Responsive Reversible Polyketone/MWCNT Network through Diels-Alder Chemistry

This study examines the preparation of electrically conductive polymer networks based on furan-functionalised polyketone (PK-Fu) doped with multi-walled carbon nanotubes (MWCNTs) and reversibly crosslinked with bis-maleimide (B-Ma) via Diels-Alder (DA) cycloaddition. Notably, the incorporation of 5 wt.% of MWCNTs results in an increased modulus of the material, and makes it thermally and electrically conductive. Analysis by X-ray photoelectron spectroscopy indicates that MWCNTs, due to their diene/dienophile character, covalently interact with the matrix via DA reaction, leading to effective interfacial adhesion between the components. Raman spectroscopy points to a more effective graphitic ordering of MWCNTs after reaction with PK-Fu and B-Ma. After crosslinking the obtained composite via the DA reaction, the softening point (tan(delta) in dynamic mechanical analysis measurements) increases up to 155 degrees C, as compared to the value of 130 degrees C for the PK-Fu crosslinked with B-Ma and that of 140 degrees C for the PK-Fu/B-Ma/MWCNT nanocomposite before resistive heating (responsible for crosslinking). After grinding the composite, compression moulding (150 degrees C/40 bar) activates the retro-DA process that disrupts the network, allowing it to be reshaped as a thermoplastic. A subsequent process of annealing via resistive heating demonstrates the possibility of reconnecting the decoupled DA linkages, thus providing the PK networks with the same thermal, mechanical, and electrical properties as the crosslinked pristine systems