Polyamide microcapsules have gathered significant research interest during the past years due to their good barrier properties; however, the potential of their application is limited due to the fragility of the polymeric membrane. Fully aliphatic polyamide microcapsules (PA MCs) were herein prepared from ethylene diamine and sebacoyl chloride via interfacial polymerization, and the effect of key encapsulation parameters, i.e., monomers ratio, core solvent, stirring rate and time during the polymerization step, were examined concerning attainable process yield and microcapsule properties (shell molecular weight and thermal properties, MC size and morphology). The process yield was found to be mainly influenced by the nature of the organic solvent, which was correlated to the diffusion potential of the diamine from the aqueous phase to the organic core through the polyamide membrane. Thus, spherical microcapsules with a size between 14 and 90 μm and a yield of 33% were prepared by using toluene as core solvent. Milder stirring during the polymerization step led to an improved microcapsule morphology; yet, the substantial improvement of mechanical properties remains a challenge.

The direct solid state polymerization (DSSP) of hexamethylene diammonium dodecanoate (PA 612 salt) was investigated for two different salt grades, fossil-based and bio-based. Aliphatic polyamide salts (such as PA 612 salt) are highly susceptible to solid melt transition (SMT) phenomena, which restrain the industrial application of DSSP. To that end, emphasis was given on reactor design, being the critical parameter influencing byproduct diffusion, amine loss and inherent DSSP kinetics. Experiments took place both at the microscale and the laboratory scale, in which two different reactors were tested in terms of bypassing SMT phenomena. The new reactor designed here proved quite successful in maintaining the solid state during the reaction. Scouting experiments were conducted in order to assess the effect of critical parameters and determine appropriate reaction conditions. Fossil-based PA 612 products proved to have a better end-group imbalance in comparison to bio-based ones, which is critical in terms of achieving high molecular weight. Finally, a real DSSP process was demonstrated, starting from PA 612 salt crystals and ending with PA 612 particles.

The present work aims to synthesize polyamide 1212 (PA 1212) via direct solid-state polymerization (DSSP), starting from its solid salt precursor. The DSSP of aliphatic polyamide salts has been found to proceed through melt intermediates, in harmony with the well-documented solid-melt transition (SMT) mechanism. However, PA 1212 salt is anticipated to deviate from this model due to its strongly hydrophobic nature. The reaction was initially investigated at the microscale in a thermo-gravimetric analysis (TGA) chamber and then scaled up to the laboratory scale. The influence of reactor design, reaction temperature, and residence time was examined. DSSP products were characterized in terms of molecular size and morphological properties. At the same time, a novel protocol was developed for qualitatively monitoring the progress of polymerization via Fourier Transform Infrared Spectroscopy-Attenuated Total Refraction (FTIR-ATR) analysis. Emphasis was given on the resulting morphology examined via Scanning Electron Microscopy (SEM imaging). Although DSSP has been found to proceed through a quasi-SMT, significant differences are observed compared to the classical mechanism established in the literature. This paper reveals that the limited surface softening or agglomeration phenomena encountered are mostly associated with the hydrophobic structure of the PA 1212 salt.