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Matteo Ceppatelli

Publications and source records attributed to Matteo Ceppatelli.

4 recordsLinked to original sources

Pressure-induced polymerization in solid ethylene.

Ethylene is the simplest organic molecule containing a double bond and is the starting monomeric unit in the synthesis of polyethylene, one of the most largely produced polymers. Here we report a high pressure infrared study of ethylene at room temperature. A polymerization reaction is observed when the crystalline phase I is compressed above 3.0 GPa. The reaction kinetics was investigated at two different pressures, 3.6 and 5.4 GPa. The recovered product was identified in both cases as polyethylene, but while a conformationally disordered and branched low-density polymer is obtained at the highest pressure, a high-density crystalline polymer is obtained at 3.6 GPa. A reaction mechanism was proposed on the basis of the kinetic data and the structural information.

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High-pressure reactivity of propene.

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.

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High-pressure synthesis of crystalline polyethylene using optical catalysis.

Polymerization processes are probably the most relevant example of a chemical reaction activated by catalysts or radical initiators. Among polymers, polyethylene is by far the most common and largely produced. Here we present a high-pressure synthesis of high-density crystalline polyethylene by using only physical tools such as pressure and light. Low-density polyethylene is obtained by compressing ethylene at room temperature above 3 GPa in the ordered crystal phase, and a highly crystalline polymer is produced in the fluid phase at pressures lower than 1 GPa by using continuous-wave laser lines (lambda < or = 460 nm) as an optical catalyst. The photo-activation is based on a two-photon absorption process to pi* antibonding states, where the change in molecular geometry favours the polymeric chain formation. The high yield and crystallinity of the polymer recovered by the photoinduced reaction and the simplicity of the synthesis make this process appealing for large-scale applications.

Journal Article↗

Laser-induced selectivity for dimerization versus polymerization of butadiene under pressure.

The pressure-induced chemical reaction of liquid butadiene was studied by Fourier transform infrared spectroscopy in a diamond anvil cell. Dimerization was found to occur above 0.7 gigapascal, giving vinylcyclohexene according to a cyclo-addiction reaction and only a trace amount of polybutadiene forms. By irradiating the high-pressure sample with a few milliwatts of the 488-nanometer argon+ laser line, the dimerization was completely inhibited, and the rapid formation of pure trans-polybutadiene was observed. The use of different excitation wavelength allows us to emphasize the selectivity of the process and to identify the active role of the 2(1)Ag state in this pressure- and laser-induced chemical reaction.

Journal Article↗