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      Sustainable Bio-Based UV-Cured Epoxy Vitrimer from Castor Oil

      , , , ,
      Polymers
      MDPI AG

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          Abstract

          Vitrimers brought new properties in thermosets by allowing their reshaping, self-healing, reprocessing, and network rearrangement without changing structural integrity. In this study, epoxidized castor oil (ECO) was successfully used for the straightforward synthesis of a bio-based solvent-free vitrimer. The synthesis was based on a UV-curing process, which proceeded at low temperatures in the absence of any solvents, and within a short time. Real time Fourier-transformed infrared spectroscopy and photo-DSC were exploited to monitor the cationic photocurable process. The UV-cured polymer networks were able to efficiently undergo thermo-activated bond exchange reactions due to the presence of dibutyl phosphate as a transesterification catalyst. Mechanical properties, thermal resistance, glass transition temperature, and stress relaxation were investigated as a function of the amount of transesterification catalyst. Mechanical properties were determined by both DMTA and tensile tests. Glass transition temperature (Tg) was evaluated by DMTA. Thermal stability was assessed by thermogravimetric analysis, whilst vitrimeric properties were studied by stress relaxation experiments. Overall, the ECO-based vitrimer showed high thermal resistance (up to 200 °C) and good mechanical properties (elastic modulus of about 10 MPa) and can therefore be considered as a promising starting point for obtaining more sustainable vitrimers.

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          Silica-like malleable materials from permanent organic networks.

          Permanently cross-linked materials have outstanding mechanical properties and solvent resistance, but they cannot be processed and reshaped once synthesized. Non-cross-linked polymers and those with reversible cross-links are processable, but they are soluble. We designed epoxy networks that can rearrange their topology by exchange reactions without depolymerization and showed that they are insoluble and processable. Unlike organic compounds and polymers whose viscosity varies abruptly near the glass transition, these networks show Arrhenius-like gradual viscosity variations like those of vitreous silica. Like silica, the materials can be wrought and welded to make complex objects by local heating without the use of molds. The concept of a glass made by reversible topology freezing in epoxy networks can be readily scaled up for applications and generalized to other chemistries.
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            • Record: found
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            Vitrimers: permanent organic networks with glass-like fluidity

            Vitrimers possess the unique property that they are malleable while being permanently cross-linked. This mini-review highlights the existing vitrimer systems in the period 2011–2015 with the main focus on their chemical origin.
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              Metal-catalyzed transesterification for healing and assembling of thermosets.

              Catalytic control of bond exchange reactions enables healing of cross-linked polymer materials under a wide range of conditions. The healing capability at high temperatures is demonstrated for epoxy-acid and epoxy-anhydride thermoset networks in the presence of transesterification catalysts. At lower temperatures, the exchange reactions are very sluggish, and the materials have properties of classical epoxy thermosets. Studies of model molecules confirmed that the healing kinetics is controlled by the transesterification reaction rate. The possibility of varying the catalyst concentration brings control and flexibility of welding and assembling of epoxy thermosets that do not exist for thermoplastics.
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                Author and article information

                Contributors
                (View ORCID Profile)
                (View ORCID Profile)
                Journal
                POLYCK
                Polymers
                Polymers
                MDPI AG
                2073-4360
                February 2023
                February 18 2023
                : 15
                : 4
                : 1024
                Article
                10.3390/polym15041024
                57842778-ce3c-4161-9ce6-be55a2739c2b
                © 2023

                https://creativecommons.org/licenses/by/4.0/

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