Pressure induced polymerization of fluid ethylene.

The spontaneous polymerization of fluid ethylene under high temperature and pressure conditions has been characterized by using FTIR absorption spectroscopy. The fluid has been isobarically heated at pressures ranging between 0.4 and 1.5 GPa by means of a resistively heated membrane diamond anvil cell. Besides tracing the instability boundary for spontaneous polymerization in the fluid, we have also measured the reaction kinetics at 1.5 GPa and temperatures ranging between 340 and 423 K. From the rate constants the activation energy of the overall reaction could be computed, information that joined to the molecularity of the initiation step provides some insight about the reaction mechanism. The polymers recovered from the different reactions have been characterized by FTIR, Raman, and X-ray diffraction revealing in all the cases a crystalline material of astonishing quality, likely related to the growth of the polymer in the hot fluid monomer.