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Mechanical properties of the prepared PI films were tested to be significantly enhanced, and the coefficient of thermal expansion decreased from 61.5 to 47.6 ppm/°C with pre-ID increasing from 0% to 100%, which could be attributed to the orderly molecular chain arrangement formed during the chemical pre-imidization process, as disclosed by MD simulation. This work paves the way for the observation of the real-time structure and property evolutions of PI materials, especially during the pre-imidization process.This Perspective of the pu