Towards new NIR dyes for free radical photopolymerization processes

The use of cheap and safe near-infrared (NIR) light is still the subject of intense research efforts but remains a huge challenge due to the associated low photon energy (wavelength from 0.78 to 2.5 µm). In this study, a series of 17 NIR dyes mainly based on a well-established cyanine scaffold is proposed. Remarkably, 11 of them were never synthesized before. Markedly, noncharged structures, negatively charged cyanine bearing Na+ as counter cation, and positively charged cyanines bearing (B(Ph)4−) or (I−) as counter anions were examined as promising NIR light photoinitiating systems. Excellent photoinitiating abilities were found for some reported dyes when used in combination with iodonium salt and amine. Markedly, photothermal effects with a huge heater behavior were also observed for different NIR dye structures. Interestingly, the synthesis of interpenetrating polymer networks (IPNs, e.g., for the polymerization of acrylate/epoxy monomer blends) can also be carried out upon NIR light with the proposed systems.

Lawsone Derivatives as Efficient Photopolymerizable Initiators for Free-Radical, Cationic Photopolymerizations, and Thiol—Ene Reactions

Two new photopolymerizable vinyl (2-(allyloxy) 1,4-naphthoquinone, HNQA) and epoxy (2-(oxiran-2yl methoxy) 1,4-naphthoquinone, HNQE) photoinitiators derived from lawsone were designed in this paper. These new photoinitiators can be used as one-component photoinitiating systems for the free-radical photopolymerization of acrylate bio-based monomer without the addition of any co-initiators. As highlighted by the electron paramagnetic resonance (EPR) spin-trapping results, the formation of carbon-centered radicals from an intermolecular H abstraction reaction was evidenced and can act as initiating species. Interestingly, the introduction of iodonium salt (Iod) used as a co-initiator has led to (1) the cationic photopolymerization of epoxy monomer with high final conversions and (2) an increase of the rates of free-radical polymerization of the acrylate bio-based monomer; we also demonstrated the concomitant thiol–ene reaction and cationic photopolymerizations of a limonene 1,2 epoxide/thiol blend mixture with the HNQA/Iod photoinitiating system.

Hydrothermal Carbon as Reactive Fillers to Produce Sustainable Biocomposites with Aromatic Bio-Based Epoxy Resins

Thiswork is focused on the development of sustainable biocomposites based on epoxy bioresin reinforced with a natural porous material (hydrochar, HC) that is the product of spruce bark wastes subjected to hydrothermal decomposition. To identify the influence of hydrochar as a reinforcing material on the designed composites, seven formulations were prepared and tested. An aromatic epoxy monomer derived from wood biomass was used to generate the polymeric matrix, and the formulations were prepared varying the filler concentration from 0 to 30 wt %. The reactivity of these formulations, together with the structural, thermal, and mechanical properties of bio-based resin and biocomposites, are investigated. Surprisingly, the reactivity study performed by differential scanning calorimetry (DSC) revealed that HC has a strong impact on polymerization, leading to an important increase in reaction enthalpy and to a decrease of temperature range. The Fourier Transform Infrared Spectroscopy (FT-IR) investigations confirmed the chemical bonding between the resin and the HC, while the dynamic mechanical analysis (DMA) showed increased values of crosslink density and of storage moduli in the biocomposites products compared to the neat bioresin. Thermogravimetric analysis (TGA) points out that the addition of hydrochar led to an improvement of the thermal stability of the biocomposites compared with the neat resorcinol diglycidyl ether (RDGE)-based resin (T5% = 337 °C) by ≈2–7 °C. Significantly, the biocomposites with 15–20 wt % hydrochar showed a higher stiffness value compared to neat epoxy resin, 92SD vs. 82SD, respectively.

A high performance fully bio-based epoxy thermoset from a syringaldehyde-derived epoxy monomer cured by furan-derived amine

Owing to the outstanding mechanical strength and modulus, high Tg, anti-flammability and anti-bacterial property, this fully bio-based epoxy thermoset is a promising substitute for DGEBA-based thermoset in high performance fire safe applications.

Nanostructured Thermoset Blends Induced by Self-assembly of Polyisoprene-bpoly(4vinyl pyridine) Diblock Copolymer Blended with Thermoset Epoxy

Nanostructured thermoset blends were prepared based on a bisphenol A-type epoxyresin and an amphiphilic reactive diblock copolymer, namely polyisopreneblockpoly(4-vinyl pyridine) (PI-P4VP). Infrared spectra revealed that the P4VP blockof the diblock copolymer reacted with the epoxy monomer. However, the non-reactivehydrophobic PI block of the diblock copolymer formed a separate microphase on thenanoscale. Ozone treatment was used to create nanoporosity in nanostructuredepoxy/PI-P4VP blends via selective removal of the PI microphase and lead tonanoporous epoxy thermosets; disordered nanopores with the average diameter of about60 nm were uniformly distributed in the blend with 50 wt% PI-P4VP. Multi-scale phaseseparation with a distinctly different morphology was observed at the air/sampleinterface due to the interfacial effects, whereas only uniform microphase separatedmorphology at the nanoscale was found in the bulk of the blend.