Study of thermal transformations and reactivity of polyacrylonitrile in heat treatment processes

To optimize the processes of obtaining graphene nanoplatelets based on polyacrylonitrile (PAN), it is necessary to study the thermal transformations and reactivity of PAN during heat treatment. The paper presents the results of a study of the thermal properties of PAN and its interaction with solvents. Using UV and IR spectroscopy, differential scanning calorimetry, thermogravimetric analysis and molecular modeling, it was found that the nitrile group CN is the key reaction center affecting the PAN structure. Calculations showed a decrease in the total energy of the system during heat treatment from 14.87 to 12.51 J/g. When PAN interacted with dimethylacetamide (DMA) and dimethylformamide (DMF), the total energy calculated per 1 atom was 6.02 and 5.64 J/g. It was also revealed that the temperature of solvent removal from the PAN/DMF film with a PAN content of 0.2 wt.% — 141.56, and the carbonization temperature is 300°C. The maximum reactivity is observed in hydrogen atoms connected to tertiary carbon atoms and located near CN groups. The combination of the applied experimental methods of analysis and molecular modeling allowed us to establish the key patterns of thermal transformations of PAN and its interaction with solvents. The results obtained can be used to improve the methods for obtaining graphene-like materials.

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