Influence of the reaction conditions on the productivity and on the molecular weight of the polyketone obtained by the CO–ethene copolymerisation catalysed by [Pd(TsO)(H 2O)(dppp)](TsO) in MeOH

• Published in: Journal of molecular catalysis. A, Chemical Vol. 276; no. 1; pp. 211 - 218
• Main Authors: Fabrello, Amandine, Vavasori, Andrea, Dall’Acqua, Federico, Toniolo, Luigi
• Format: Journal Article
• Language: English
• Published: Amsterdam Elsevier B.V 17.10.2007; Elsevier
• Subjects: Applied sciences; Carbon monoxide; Copolymerisation; Copolymerization; Dppp; Ethene; Exact sciences and technology; Molecular weight; Organic polymers; Palladium catalyst; Physicochemistry of polymers; Polyketone; Preparation, kinetics, thermodynamics, mechanism and catalysts; Ethene; Palladium catalyst; Polyketone; Carbon monoxide; Dppp; Molecular weight; Copolymerisation; Palladium II Complexes; Conversion rate; Ethylene; Ketone polymer; Experimental study; Complex catalyst copolymerization; Ditertiary phosphine; Aliphatic polymer; Alternating copolymerization; Processing parameter; Kinetics
• ISSN: 1381-1169; 1873-314X
• DOI: 10.1016/j.molcata.2007.07.005

The influence of the pressure of the monomers, of the temperature and of the reaction time on the productivity on the CO–ethene copolymerisation catalysed by the title complex used in combination with TsOH and on the molecular weight of the resulting polyketone has been studied, together with the influence of the TsOH/Pd ratio. A power law rate equation for the productivity has been obtained. The results are discussed on the light of the mechanism of the copolymerisation reaction. ▪ The influence of the operating conditions on the productivity on the CO–ethene copolymerisation catalysed by the title complex used in combination with TsOH and on the average numerical molecular weight, the limiting viscosity number and the average viscosity molecular weight of the resulting polyketone has been studied. The productivity, LVN and M ¯ v pass through a maximum for a TsOH/Pd ratio = 6/1, whereas M ¯ n reaches a plateau and remains practically constant at higher acid concentration. They increase upon increasing the pressures of the monomers when employed in the ratio 1/1 as well as upon increasing the pressure of CO keeping constant the pressure of the other monomer; the productivity as well as M ¯ n increase, whereas the LVN and M ¯ v pass through a maximum upon increasing the pressure of ethene, keeping constant the pressure of CO. A power law rate equation for the productivity has been obtained. The productivity decreases whereas the molecular weights increase upon lowering the temperature; the productivity decreases upon increasing the reaction time, whereas the molecular weights are little influenced. The results are discussed in the light of the copolymerisation mechanism.