Cooligomerization using peroxide initiators (initiated co-oligomerization) is widely used in industry. It allows to obtain cooligomers (hydrocarbon resins) high yield and good properties. The disadvantage of radical co-oligomerization is the high temperature of the process (453-473 K) and the complexity of the target product. The hydrocarbon resin is separated by distillation from a solution of unpolymerized fraction components.
The disadvantages of the industrial method of radical co-oligomerization of the C9 fraction can be eliminated by using low-temperature dispersion co-oligomerization.
Dispersion (emulsion / suspension) co-oligomerization of unsaturated hydrocarbons of C9 fraction ensures maximum yield of the product - up to 20.0% by weight. in terms of fraction C9. Chromatographic analysis revealed that at this stage, the styrene monomers and their derivatives are introduced into the cooligomerization reaction. In the reaction mixture remaining after the separation of the co-oligomer and distillation of the precipitant there are high-boiling reactive dicyclopentadiene, indene, residual styrene and its derivatives.
At temperatures 453-463 K, a cycle is revealed (monomerization) of the dicyclopentadiene (DCPD) with the formation of two reactive cyclopentadiene (CPD) monomers.
Authors propose a two-step synthesis method. The first stage - dispersion (suspension / emulsion) fraction C9 hydrocarbons co-oligomerization in the temperature range 333-353 K. At this stage, a styrenic (co)oligomer is obtained. The second stage is the thermal / initiation post-cooligomerization of unreacted hydrocarbons from the first stage. The temperature of the process is 453 K. At this stage, a cyclopentadiene co-oligomer with a small number of parts of other unsaturated hydrocarbons of the C9 fraction is obtained.
Infrared spectroscopy of the obtained co-oligomers was performed. It has been established that the CPD (co)oligomer contains insignificant amounts of styrene and vinyl-toluene units that did not react at the first stage of the process
The water and chemical stability of the CPD cooligomer were investigated.
The possibility of synthesis of cyclopentadiene (co)oligomers on the basis of organic residues of emulsion and suspension oligomerization was established. A comparative evaluation of the physical and chemical characteristics of cyclopentadiene resins is carried out by different methods.
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