The phase diagram of propene has been investigated at high pressure by using the diamond anvil cell technique and Fourier transform infrared spectroscopy. The pressure conditions necessary to induce a spontaneous reaction of the sample have been found at different temperatures, allowing the stability boundary of propene to be drawn. The reaction is diffusion controlled and seems to occur only in the fluid phase, implying a slope inversion of the stability boundary at about 250 K. The product of the reaction is a mixture of linear oligomers independently of the P-T conditions. The activation volume and energy of the process have been obtained from the kinetic data. Also the activation of the reaction by laser absorption has been carefully studied. A high proton mobility has been identified as the likely reason that limits the lengthening of the chain up to six to eight monomeric units preventing the polymer formation.