A coating from nature

For almost a century, petrochemical-based monomers like acrylates have been widely used as the basis for coatings, resins, and paints. The development of sustainable alternatives, integrating the principles of green chemistry in starting material, synthesis process, and product function, offers tremendous challenges for science and society. Here, we report on alkoxybutenolides as a bio-based alternative for acrylates and the formation of high-performance coatings. Starting from biomass-derived furfural and an environmentally benign photochemical conversion using visible light and oxygen in a flow reactor provides the alkoxybutenolide monomers. This is followed by radical (co) polymerization, which results in coatings with tunable properties for applications on distinct surfaces like glass or plastic. The performance is comparable to current petrochemical-derived industrial coatings

Electron-Poor Butenolides:The Missing Link between Acrylates and Maleic Anhydride in Radical Polymerization

Butenolides are a class of 5-membered lactones that hold great potential as bio-based monomers to replace oil-derived acrylates, of which they are cyclic analogues. Despite this structural resemblance, the reactivity of the unsaturated ester moiety of electron-poor butenolides leans toward that of maleic anhydride, another essential monomer that does not homopolymerize but copolymerizes in a highly alternating fashion with polarized electron-rich comonomers. By studying the reactivity of 5-methoxy and 5-acyloxy butenolides through a combination of kinetics and density functional theory (DFT) experiments, we explain why electron-poor butenolides constitute a missing link between acrylates and maleic anhydride in radical polymerization.</p

A sustainable polymer and coating system based on renewable raw materials

Paints and coatings are widely used in modern society and their current production is mainly dependent on the petrochemical industry. The establishment of processes using sustainable alternative monomers based on biorenewable resources, using exclusively biobased reagents and green synthetic transformations are highly warranted for a more sustainable future. Herein, we report on a sustainable polymer and coating system based on the monomer methoxybutenolide, a biobased acrylate alternative. Methoxybutenolide and the comonomer dodecyl vinyl ether are synthesized from biobased platform chemicals using the environmentally benign synthetic transformations photooxygenation and vinylation. For the photooxygenation, a biobased photosensitizer was developed showing high quantum yields. The monomers were copolymerized using biomass derived (photo)initiators to yield fully biobased polymers and coatings with properties comparable to acrylate based coatings

Mechanistic elucidation of monoalkyltin(iv)-catalyzed esterification

Monoalkyltin(iv) complexes are well-known catalysts for esterification reactions and polyester formation, yet the mode of operation of these Lewis acidic complexes is still unknown. Here, we report on mechanistic studies of n-butylstannoic acid in stoichiometric and catalytic reactions, analyzed by NMR, IR and MS techniques. While the chemistry of n-butyltin(iv) carboxylates is dominated by formation of multinuclear tin assemblies, we found that under catalytically relevant conditions only monomeric n-BuSn(OAc)(3) and dimeric (n-BuSnOAc(2)OEt)(2) are present. Density functional theory (DFT) calculations provide support for a mononuclear mechanism, where n-BuSn(OAc)(3) and dimeric (n-BuSnOAc(2)OEt)(2) are regarded as off-cycle species, and suggest that carbon–oxygen bond breaking is the rate-determining step

<i>In situ</i> EPR and Raman spectroscopy in the curing of bis-methacrylate-styrene resins

The curing of bis-methacrylate-styrene resins initiated by the cobalt catalyzed decomposition of cumyl hydroperoxide is monitored at ambient temperatures in situ by EPR and Raman spectroscopy. EPR spectroscopy shows the appearance of organic radicals after ca. 1 h from initiation with an increase in intensity from both polystyrene and methacrylate based radical species over a further ca. 2 h period to reach a maximum spin concentration of ca. 2-3 mM. Alkene conversion to polymer was monitored by Raman spectroscopy in real time in situ with EPR spectroscopy and reveals that the appearance of the radical signals is first observed only as the conversion approaches its maximum extent (70% at room temperature), i.e., the resin reaches a glass-like state. The radicals persist for several months on standing at room temperature. Flash frozen samples (77 K) did not show EPR signals within 1 h of initiation. The nature of the radicals responsible for the EPR spectra observed were explored by DFT methods and isotope labelling experiments (D8-styrene) and correspond to radicals of both methacrylate and polystyrene. Combined temperature dependent EPR and Raman spectroscopy shows that conversion increases rapidly upon heating of a cured sample, reaching full conversion at 80 °C with initially little effect on the EPR spectrum. Over time (i.e. subsequent to reaching full conversion of alkene) there was a small but clear increase in the EPR signal due to the methacrylate based radicals and minor decrease in the signal due to the polystyrene based radicals. The appearance of the radical signals as the reaction reaches completion and their absence in samples flash frozen before polymerization has halted, indicate that the observed radicals are non-propagating. The formation of the radicals due to stress within the samples is excluded. Hence, the observed radicals are a representative of the steady state concentration of radicals present in the resin over the entire timespan of the polymerization. The data indicate that the lack of EPR signals is most likely due to experimental aspects, in particular spin saturation, rather than low steady state concentrations of propagating radicals during polymerization.</p

A highly efficient and sustainable catalyst system for terminal epoxy-carboxylic acid ring opening reactions

The nucleophilic ring opening of epoxides by carboxylic acids is an indispensable transformation for materials science and coating technologies. Due to this industrial significance, improvements in operational energy consumption and catalyst sustainability are highly desirable for this transformation. Herein, an efficient, environmentally benign and non-toxic halide free cooperative catalyst system based on an iron(III) benzoate complex and guanidinium carbonate is reported. The novel catalyst system shows improved activity over onium halide catalysts under neat conditions and in several solvents, including anisole and nBuOAc. Detailed mechanistic studies using FeCl3/DMAP as a catalyst revealed the importance of a carboxylate bridged cationic trinuclear μ3-oxo iron cluster and guanidinium carbonate or DMAP as a carboxylate reservoir due to its superior activity.</p

A highly efficient and sustainable catalyst system for terminal epoxy-carboxylic acid ring opening reactions

The nucleophilic ring opening of epoxides by carboxylic acids is an indispensable transformation for materials science and coating technologies. Due to this industrial significance, improvements in operational energy consumption and catalyst sustainability are highly desirable for this transformation. Herein, an efficient, environmentally benign and non-toxic halide free cooperative catalyst system based on an iron(III) benzoate complex and guanidinium carbonate is reported. The novel catalyst system shows improved activity over onium halide catalysts under neat conditions and in several solvents, including anisole and nBuOAc. Detailed mechanistic studies using FeCl3/DMAP as a catalyst revealed the importance of a carboxylate bridged cationic trinuclear μ3-oxo iron cluster and guanidinium carbonate or DMAP as a carboxylate reservoir due to its superior activity.</p

Regioselective palladium-catalysed aerobic oxidation of dextran and its use as a bio-based binder in paperboard coatings

The coatings industry is aiming to replace petrochemical-based binders in products such as paints and lacquers with bio-based alternatives. Native polysaccharide additives are already used, especially as adhesives, and here we show the use of oxidised dextran as a bio-based binder additive. Linear dextran with a molecular weight of 6 kDa was aerobically oxidised in water at the C3-position of its glucose units, catalysed by [(neocuproine)PdOAc]2(OTf)2. The resulting keto-dextran with different oxidation degrees was studied using adipic dihydrazide as a crosslinker in combination with the commercial petrochemical-based binder Joncryl®. Coating experiments show that part of the Joncryl® can be replaced by keto-dextran while maintaining the desired performance.</p