Abstract
New catalyst systems based on alkylaluminum derivatives and halogen or interhalogen compounds were found highly efficient in the synthesis of high-molecular-weight IIR at temperatures above − 50°C. The reaction mechanism was studied in detail for the system Et2AlCl + Cl2. The reactions occurring between chlorine, isobutene, Et2AlCl, and the solvent (CH3Cl) were elucidated and studied under various experimental conditions (e.g. presence or absence of light, simultaneous presence of the copolymerization system components, temperature, type of halogen, use of model compound of isobutene). It was concluded that halogenium ions, i.e. Cl+, Br+, or I+, are the initiating species. Kinetic and conductometric investigations showed that scarcely dissociated ion pairs, e.g. Cl+[Et2AlCl2]−, were formed in the absence of monomer; but in the presence of isobutene, a noticeable increase of the electrical conductivity and rapid polymerization occurred. The maximum polymerization rate was first order with respect to the concentrations of monomer, Cl2, and Et2AlCl. In the homopolymerization of isobutene, transfer to monomer and termination reactions were negligible. The MW of IIR was found to be mainly dependent on the concentrations of the catalyst components, on isoprene concentration, and on temperature. The reactivity ratio of isobutene with isoprene was found to be r1=2.5±0.5 at −35°C, while the activation energies relative to MW were −5.8 ± 0.4, kcal/mol for polyisobutene, and −5.7 ± 0.7 and − 4.3 ± 0.5 kcal/mol for IIR containing, respectively, 1.3 and 1.9 mol% of isoprene. The evaluation of some physicochemical and technological properties of typical IIR produced with the system Et2AlCl + Cl2, indicated that isoprene is randomly distributed along the chains and that the MWD is monomodal, while the glass transition temperature, tensile properties, mechanical-dynamic spectra, and kinetics of vulcanization are very similar to those of commercial IIR. Very preliminary data, referring to several classes of new catalyst systems yielding IIR having good properties, were also obtained. The syncatalyst systems here described can work in a homogeneous phase consisting of an aliphatic hydrocarbon besides methyl chloride, still giving IIR with high MW. Therefore, a completely homogeneous process can be envisioned for the synthesis of IIR at −50°C thus avoiding a great part of the fouling problems of the slurry process. The economic advantage of using “high” temperatures of polymerization is briefly discussed in terms of energy savings.
Voltammetric oxidation of dipyridamole in aqueous acid solutions