4.7 Article

Thermolysis and analysis of TDI char by supercritical methanol using TGA, DSC, IR and SEM

Journal

JOURNAL OF THERMAL ANALYSIS AND CALORIMETRY
Volume 146, Issue 5, Pages 2323-2331

Publisher

SPRINGER
DOI: 10.1007/s10973-020-10336-3

Keywords

Polymer char; Depolymerization; Methanolysis; Supercritical fluid; Polymer degradation

Funding

  1. Science and Technology Development Foundation of ZTRI [332017CA0160, 332012CA0080]
  2. National Natural Science Foundation of China [51878171]
  3. Scientific Research Foundation of Fuzhou [2019-G-51]
  4. Scientific Research Foundation of the Education Department of Fujian Province [JAT190427]
  5. Scientific Research Foundation of Fujian University of Technology [GY-Z160041, GY-Z160042]

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This study has discovered an effective method for depolymerizing TDI char using supercritical methanol, achieving efficient destruction of the polymer. Through various experimental methods, it was found that the optimal result can be achieved at 270 degrees Celsius, and compared to other treatment methods, supercritical methanolysis has superior depolymerization capability.
TDI's synthetic plant generates about 5 mass % of tar by phosgenation process, which has been currently a bottleneck needed to be broken through for the worldwide TDI companies. At present, the reduction fraction of TDI tar is up to 48% relative to the mass of tar and renders the residue of solid crust known as TDI char. In this study, a suasive and effective reduction method has been found, the supercritical methanol is executed to depolymerize the TDI char, and in short, the char can be readily methanolyzed at supercritical state of methanol. With the outstanding depolymerization capability than various existing approaches, the destruction fraction can achieve 81 mass % at supercritical point. A best value as high as 95 mass % is first discovered at 270 degrees C, exceeding the efficiency at supercritical state. Characterizations of the intrinsic properties of raw char and char remnant after methanolysis have been implemented by TGA, DSC, FT-IR and SEM-EDS. For industrial applications, the diverse methodologies for recovering TDI or related components by alkaline hydrolysis, distillation, vacuum distillation and thermolysis are also discussed and compared with methanolysis in order to recognize the optimal abatement technique.

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