Anionic polymarisation of caprolactam: an approach to optimising thr polymerisation condition to be used in the jetting process
thesisposted on 13.05.2011, 08:20 by Khosrow Khodabakhshi
The main aim of this project was to investigate the possibility of manufacturing 3D parts of polyamide (nylon or PA) 6 by inkjetting its monomer caprolactam (CL). The principle of this process was similar to the other rapid prototype (RP) and rapid manufacturing (RM) processes in which a 3D part is manufactured by layer on layer deposition of material. PA6 was used as the thermoplastic polymer in this work because of its good properties and also because PA6 can be produced by heating its monomer (i.e. plus catalyst and activator) in a short time. Two polymerisation mixtures of CL-catalyst (mixture A) and CL-activator (mixture B) are intended to be jetted separately using conventional jetting heads and polymerise shortly after heating. Anionic polymerisation of CL (APCL) was investigated in the bulk and on a smaller scale. Sodium caprolactamate (CLNa and C10) and caprolactam magnesium bromide (CLMgBr) were used as catalysts and N-acetylcaprolactam (ACL) and a di-functional activator (C20) were used as activators. The influence of polymerisation conditions was investigated and optimised. These were catalyst-activator concentration, polymerisation temperature and the influence of the polymerisation atmosphere. The physical properties (monomer conversion, crystallinity, and viscosity average molecular weight) of PA6 samples produced using each catalyst-activator combinations were measured and compared. Small scale polymerisation was carried out using a hotplate, by hot stage microscopy and using differential scanning calorimetry (DSC). The influence of heating strategy on small scale polymerisation was studied using DSC. The polymerisation mixture compositions were characterised using rheometry, Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and optical microscopy to investigate their suitability in jetting for using the available jetting heads. It was shown that the combination of CLMgBr-ACL resulted in fast polymerisation which was not sensitive to moisture. The C10-C20 combination resulted in fast polymerisation with the best properties in a protected environment (nitrogen); however, the polymerisation was affected by moisture in air and the properties of polymer produced and rate of polymerisation decreased in air. Polymers produced using CLNa-ACL had the poorest properties and polymerisation did not occur in air. Material characterisation showed that micro-crystals of CLMgBr existed in CLMgBr-CL mixture at the jetting temperature (80oC) which were too large to be jetted. However, the mixture of C10 in CL could be partially jetted. The activator mixtures had similar properties to CL and were easily jetted. Drop on drop polymerisation was carried out by dripping droplets of mixtures A and B (at 80oC) on top of each other on a hotplate at the polymerisation temperature. Small scale polymerisation in a DSC showed that the monomer conversion increased with increase in polymerisation temperature from 140oC to 180oC and decreased from 180oC to 200oC. The crystallinity of the polymer produced in the DSC decreased with increase in polymerisation temperature. Hot stage microscopy produced evidence for simultaneous polymerisation and crystallisation processes on heating. Small scale polymerisation in an oven and analysed by DSC showed that increasing catalystactivator concentration resulted in increasing monomer conversion and decrease in crystallinity. Monomer conversion also increased with increase in polymerisation temperature and polymerisation time. Comparison between small scale and bulk polymerisations shows a good agreement between the two polymerisation rates. This shows that the polymerisation mechanism did not change significantly when the quantity of materials was reduced to less than 20mg. Finally, the polymerisation was carried out in a DSC after jetting C10-CL and C20-CL mixtures into a DSC pan using a jetting system, which was made in another work.
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