The peculiar reactivity of catechol carbonate (CC) with amines and polyamines in both solvent-and catalyst-free conditions is herein described. In all the tests performed at room temperature, CC conversion reached 100% in a few seconds leading to the selective formation of the corresponding 2hydroxyphenylcarbamate. This compound is further rapidly converted to the disubstituted urea by the consecutive nucleophilic attack of another amine. Noteworthy, the application of this approach can be successfully extended to the one-pot bioaminebased synthesis of polyurea as herein proposed for the first time in the literature. The reaction is of general purpose for primary amines, and catechol can be easily recovered by sublimation as pure crystals ready to be recycled for the synthesis of new CC. An exception is related to the reactivity of secondary amine, which leads to the selective formation of substituted phenolic carbamates (e.g., 2-hydroxyphenyl diethylcarbamate), suitable as intermediates in medicinal chemistry.

Considering the current context of research aiming at proposing new bioplastics with low costs and properties similar to fossil-based commodities currently on the market, in the present work, a hybrid blend containing a prevalent amount of cheap inedible cereal flour (70 wt %) and poly(butylene succinate) (PBS) (30 wt %) has been prepared by a simple, eco-friendly, and low-cost processing methodology. In order to improve the interfacial tension and enhance the adhesion between the different phases at the solid state, with consequent improvement in microstructure uniformity and in material mechanical and adhesive performance, the PBS fraction in the blend was replaced with variable amounts (0–25 wt %) of PBS-based green copolymer, which exerted the function of a compatibilizer. The copolymer is characterized by an ad hoc chemical structure, containing six-carbon aliphatic rings, also present in the flour starch structure. The two synthetic polyesters obtained through two-stage melt polycondensation have been deeply characterized from the molecular, thermal, and mechanical points of view. Copolymerization deeply impacts the polymer final properties, the crystallizing ability, and stiffness of the PBS homopolymer being reduced. Also, the prepared ternary blends were deeply investigated in terms of microstructure, thermal, and mechanical properties. Lastly, both pure blend components and ternary blends were subjected to disintegration experiments under composting conditions. The results obtained proved how effective was the compatibilizer action of the copolymer, as evidenced by the investigation conducted on morphology and mechanical properties. Specifically, the mixtures with 15 and 20 wt % Co appeared to be characterized by the best mechanical performance, showing a progressive increase of deformation while preserving good values of elastic modulus and stress. The disintegration rate in compost was found to be higher for the lower amount of copolymer in the ternary blend. However, after 90 days of incubation, the blend richest in copolymer content lost 62% of weight.

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Tammann’s two-stage crystal-nuclei-development method is applied for analysis of the thermal stability of homogenously formed crystal nuclei of poly(butylene isophthalate) (PBI) as well as their possible reorganization on transferring them to the growth temperature, using fast scanning chip calorimetry. Crystal nuclei were formed at 50 °C, that is, at a temperature only slightly higher than the glass transition temperature, and developed to crystals within a pre-defined time at the growth temperature of 85 °C. The number of nuclei, overcritical at the growth temperature, was detected as a function of the transfer-conditions (maximum temperature, heating rate) by evaluation of the developed crystal fraction. For different size-distributions of crystal nuclei, as controlled by the nucleation time, there is detected distinct reduction of the nuclei number on heating to maximum temperatures higher than about 90 to 110 °C, with the latter value holding for longer nucleation time. Longer nucleation allows for both increasing the absolute nuclei number and generation of an increased fraction of larger nuclei. Heating at 1000 K/s to 140–150 °C causes “melting” of even the most stable nuclei. While direct transfer of crystal nuclei from the nucleation temperature (50 °C) to the growth temperature (85 °C) reveals negligible effect of the transfer-heating rate, in-between heating to higher temperatures is connected with distinct nuclei-reorganization above 85 °C on heating slower than 1000–10.000 K/s. The performed study not only provides specific valuable information about the thermal characteristics of crystal nuclei of PBI but also highlights the importance of proper design of Tammann’s nuclei development experiment for analysis of nuclei numbers. With the evaluation of critical rates of temperature-change for suppression of non-isothermal formation of both nuclei and crystals, the kinetics of crystallization of the slow crystallizing PBI is further quantified.