Polymer-supported chiral organocatalysts, as well as most other forms of immobilized catalysts, are traditionally prepared by a postmodification approach where modified catalyst precursors are anchored onto prefabricated polymer beads. Herein, we report an alternative and more scalable approach where polymer-supported chiral enamine and iminium organocatalysts are prepared in a bottom-up fashion where methacrylic functional monomers are prepared in an entirely nonchromatographic manner and subsequently copolymerized with suitable comonomers to give cross-linked polymer beads. All syntheses have been conducted on multigram scale for all intermediates and finished polymer products, and the catalysts have proven successful in reactions taking place in solvents spanning a wide range of solvent polarity. While polymer-supported proline and prolineamides generally demonstrated excellent results and recycling robustness in asymmetric aldol reactions of ketones and benzaldehydes, the simplest type of Jørgensen/Hayashi diarylprolinol TMS-ether showed excellent selectivity, but rather sluggish reactivity in the Enders-type asymmetric cascade. The polymer-supported version of the first-generation MacMillan imidazolidinone had a pattern of reactivity very similar to that of the monomeric catalyst, but is too unstable to allow recycling.

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Inorganic extenders are important constituents of 2K thermosetting epoxy-amine coatings and their physical properties play an important role in the final properties of the organic coatings. The effects of extender particle size and loading (i.e., the amount of extender in component A or in the total formulation) on the glass transition temperature (Tg) of model epoxy-amine coatings were studied in this work with differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). The obtained results show that the particle size and loading of feldspar particles (from 25 wt% to 70 wt%) do not influence the glass transition temperature of the model epoxy-amine coating significantly. In general, the smaller the particle size the lower the glass transition temperature of the coating but this depression in Tg seems negligible when seen relative to the change in extender particle size. Similar observations are reported for two model coatings having the same lamda (Λ) value but with silica of very different particle sizes (i.e., nanosilica and micron sized silica).

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