Abstract. The curing of bisphenol A-aniline based benzoxazine was studied applying different accelerators (4,4"-thiodiphenol, o-dianisidine, 2-mercaptobenzimidazole and 4-mercaptophenol) to initiate the catalytic ring-opening of benzoxazine. Possible pathways of benzoxazine ring-opening, polymerization and cross-linking without and with the addition of different accelerators are presented. The curing kinetics was investigated by model-free kinetic analysis of experimental data obtained by differential scanning calorimetry (DSC). The addition of different accelerators significantly reduced the onset temperature of curing in dynamic experiments. The effects of accelerators on the results of isothermal conversion prediction were studied and discussed in detail. Among the used accelerators, thiodiphenol showed the best accelerating efficiency and was consequently used in further studies, where its amount was varied. By low heating rate DSC analysis the catalytic ring-opening, thermally accelerated ring-opening and the diffusion-controlled steps were identified. The amount of added accelerator affected particularly the ring-opening and diffusion-controlled steps.
Abstract. The object of this study was to investigate how different decreasing of pH regimes during microencapsulation process with melamine-formaldehyde (MF) resin affects the composition, morphology and thermal stability of microcapsules containing a phase-change material (PCM). Technical butyl stearate was used as PCM. Microencapsulation was carried out at 70°C. For all experiments the starting pH value was 6.0. After one hour of microencapsulation at the starting pH value, the pH value was lowered to final pH value (5.5; 5.0; 4.5) in a stepwise or linear way. The properties of microcapsules were monitored during and after the microencapsulation process. The results showed that pH value decreasing regime was critical for the morphology and stability of microcapsules. During microencapsulations with a stepwise decrease of pH value we observed faster increase of the amount of MF resin in the microencapsulation product compared to the microencapsulations with a linear pH value decrease. However, faster deposition in the case of microencapsulations with stepwise decrease of pH value did not result in thicker MF shells. The shell thickness increased much faster when the pH value was decreased in a linear way or in several smaller steps. It was shown that for the best thermal stability of microcapsules, the pH value during microencapsulation had to be lowered in a linear way or in smaller steps to 5.0 or lower.
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