We developed thermally self-healing polymeric materials on the basis of furan-functionalized, alternating thermosetting polyketones (PK-furan) and bis-maleimide by using the Diels-Alder (DA) and Retro-Diels-Alder (RDA) reaction sequence. PK-furan can be easily obtained under mild conditions by the Paal-Knorr reaction of the polyketones with furfurylamine. The highly cross-linked polymers can be thermally remended to complete recovery in fracture loading, whereas the remending process can be repeated multiple times without any loss in mechanical properties. It is found that the achieved self-healing ability of this easily accessible system provides full recyclability and reworkability, which often is perceived to be difficult or impossible for thermosetting polymers. The simplicity of the synthesis, the broad range of available polyketone precursors, and the striking healing ability (kinetics and efficiency of mechanical properties recovery) of this system could expand the scientific understanding of self-healing materials and introduce the cradle-to-cradle concept for thermoset-based plastics and composites.
The reaction between carbon dioxide and epoxides is an attractive pathway for CO2-utilisation as it can lead to the formation of two valuable products: cyclic and polymeric carbonates.
A proof
of principle for the use of Diels–Alder chemistry
as a thermoreversible cross-linking tool for rubber products is demonstrated.
A commercial ethylene-propylene rubber grafted with maleic anhydride
has been thermoreversibly cross-linked in two steps. The pending anhydride
rings were first modified with furfurylamine to graft furan groups
onto the rubber backbone. These pending furans were cross-linked with
a bismaleimide via a Diels–Alder coupling reaction. The newly
formed Diels–Alder cross-links break at elevated temperatures
(>150 °C) and can be re-formed by thermal annealing (50–70
°C). Reversibility of the rubber network was proven with infrared
spectroscopy and on the basis of the mechanical properties. Furthermore,
reversibility was also shown in a practical way, i.e., by cutting
the used material into pieces and pressing them into new samples displaying
comparable mechanical properties (impossible for conventionally cross-linked
rubbers). The physical properties of the resulting products are comparable
to those of conventionally cross-linked EPDM rubber and superior compared
to those of their non-cross-linked precursors.
Supercritical carbon dioxide (CO 2) is well established for use as a processing solvent in polymer applications such as polymer modification, formation of polymer composites, polymer blending, microcellular foaming, particle production and polymerization. Its gas-like diffusivity and liquid-like density in the supercritical phase allow replacing conventional, often noxious, solvents with supercritical CO 2. Though only a few polymers are soluble in supercritical CO 2 , it is quite soluble in many molten polymers. CO 2 dissolution in a polymer has been interpreted physically but FT-IR studies lead to an explanation in terms of weak interactions between basic and acidic sites. Various experimental methods and equations of state are available to measure or predict the solubility of CO 2. Dissolved CO 2 causes a considerable reduction in the viscosity of molten polymer, a very important property for the applications stated above. CO 2 mainly acts as a plasticizer or solvent when contacted with a polymer. Gas solubility and viscosity reduction can be predicted theoretically from purecomponent properties. In this review, experimental and theoretical studies of solubility and viscosity of several polymer melts are discussed in detail. Detailed attention is also given to recently reported applications along with aspects related to polymer processing.
Homogeneuosly sulfonated poly(styrene) (SPS) was prepared with various concentration of sulfonic acid groups in the base polymer. Membranes cast from these materials were investigated in relation to proton conductivity and methanol permeability in the temperature range from 20 • C to 60 • C. It was found that both these properties increase as the polymer is increasingly sulfonated, with abrupt jumps occurring at a concentration of sulfonic acid groups of about 15 mol%. The most extensively sulfonated membrane exhibited conductivity equal to that of Nafion. As a consequence, this membrane material is potentially an appealing alternative to the very expensive Nafion, for a number of electrochemical applications. For the membrane with the highest degree of sulfonation we measured a methanol permeability about 70% smaller than for Nafion. This characteristic is especially desirable in applications related to the direct methanol fuel cell (DMFC).
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