Light-induced catalyst and solvent-free high pressure synthesis of high density polyethylene at ambient temperature

The combined effect of high pressure and electronic photo-excitation has been proven to be very efficient in activating extremely selective polymerisations of small unsaturated hydrocarbons in diamond anvil cells (DAC). Here we report an ambient temperature, large volume synthesis of high density polyethylene based only on high pressure (0.4-0.5 GPa) and photo-excitation (~350 nm), without any solvent, catalyst or radical initiator. The reaction conditions are accessible to the current industrial technology and the laboratory scale pilot reactor can be scaled up to much larger dimensions for practical applications. FTIR and Raman spectroscopy, and X-ray diffraction, indicate that the synthesised material is of comparable quality with respect to the outstanding crystalline material obtained in the DAC. The polydispersity index is comparable to that of IV generation Ziegler-Natta catalysts. Moreover the crystalline quality of the synthesised material can be further enhanced by a thermal annealing at 373 K and ambient pressure. High density polyethylene is synthesised at ambient temperature using only pressure and near-UV photons, without any solvent, catalyst or radical initiator. The reaction conditions are accessible to the current industrial technology and the dimensions of the laboratory scale pilot reactor can be scaled up for practical applications. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.