Wavelength-Dependent Activation of Photoacids and Bases.

Photoacids and bases allow remote control over pH in reaction solutions, which is of fundamental importance to an array of applications. Herein, we determine the wavelength-by-wavelength resolved photoreactivity of triarylsulfonium hexafluorophosphate salts as a representative photoacid generator and p-(benzoyl)benzyl triethylammonium tetraphenylborate as a photobase generator, constructing a wavelength-resolved photochemical action plot for each of the compounds. We monitor the pH change of the solution on-line within the cavity of the laser vial and demonstrate a marked mismatch between the absorption spectrum of the photoacid and base with the photochemical action plot, unveiling reactivity at very low absorptivities. Our findings are of critical importance for the use of photoacids and bases, unambiguously demonstrating that absorption is no guide to chemical reactivity with critical consequences for the wavelength employed in applications of photoacids and bases.

Chemical Recycling of Flexible Polyurethane Foams by Aminolysis to Recover High-Quality Polyols.

Polyurethane foams (PUFs) are widely used commodity materials, but most of them end up in landfills at the end of their life, which is not in line with the circular economy approach. Here, we introduce microwave-assisted aminolysis with amine reagents that contain primary and tertiary amino groups in the structure. These reagents enable complete degradation of the urethane groups in the structure of the flexible PUFs with a much lower amount of degradation reagent than is typically required for solvolysis reactions. The purified, recovered polyols are close equivalents to the corresponding virgin polyols in terms of their structural and molar mass characteristics. Therefore, they can be used for the production of high-quality PUFs without having to adapt the synthesis process. The flexible PUFs made from recovered polyols have comparable mechanical properties to those made from virgin polyols.

Insight into Chemical Recycling of Flexible Polyurethane Foams by Acidolysis.

Acidolysis is emerging as a promising method for recycling polyurethane foam (PUF) waste. Here, we present highly efficient acidolysis of PUFs with adipic acid (AA) by heating the reaction mixtures with microwaves. The influence of experimental conditions, such as reaction temperature, time, and amount of the degradation reagent, on the polyol functionality, molecular weight characteristics, the presence of side products, and the degree of degradation of the remaining PUF hard segments was studied by matrix-assisted laser desorption/ionization time-of-flight mass spectroscopy (MALDI-TOF MS), nuclear magnetic resonance (NMR), size-exclusion chromatography (SEC) coupled to a multidetection system, and Fourier transform infrared (FT-IR) spectroscopy. The purified recycled polyols were used for the synthesis of flexible PUFs. The morphology and mechanical properties of the PUFs show that the degree of functionalization of the polyol by the carboxylic end groups, which is higher for larger amounts of AA used to degrade the PUFs, significantly affects the quality and performance of the flexible PUFs from the recycled polyols.

Porous Polystyrene Monoliths Prepared from in Situ Simultaneous Interpenetrating Polymer Networks: Modulation of Morphology by Polymerization Kinetics.

Semi-interpenetrating polymer networks (semi-IPNs) were prepared by in situ simultaneous orthogonal polymerizations, where the linear poly(ε-caprolactone) (PCL) was synthesized by ring-opening polymerization of ε-caprolactone and the poly(styrene-co-divinylbenzene) (PS) network was formed by free-radical polymerization of styrene/divinylbenzene. Semi-IPNs were used as the precursors for the preparation of porous PS monoliths. To this end, the PCL domains were selectively removed by hydrolysis under basic conditions. By changing the amount of organocatalyst used for the ring-opening polymerization of ε-caprolactone, the relative polymerization kinetics of both monomers was varied, which has a pronounced effect on the morphology of thus-obtained PS frameworks.