CYCLOPENTADIENE OLIGOMER SYNTHESIS BASED ON C9 FRACTION OF LIQUID PYROLYSIS PRODUCTS

2018;
102-106
1
Lviv Polytechnic National University
2
Lviv Polytechnic National University
3
Lviv Polytechnic National University
4
Lviv Polytechnic National University

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.

1. Fuch U. Study of emulsifier nature effect on the process of hydrocarbon fraction
cooligomerization in the emulsion / U. Fuch, B. Dzinyak, R. Subtelnyy // Eastern European Journal of
Enterprise Technologies. – 2015. – Vol. 4(6). – P. 54–57. 2. Orobchuk O. M. Dyspersiina
koolihomeryzatsiia sumishi nenasychenykh vuhlevodniv fraktsii C9: avtoref. dys. na zdobuttia stupenia
kand. tekhn. nauk: spets. 05.17.04 “Tekhnolohiia produktiv orhanichnoho syntezu” / O. M. Orobchuk. –
Lviv, 2015. – 2015. – 21 s. 3. Xiong Zhongqiang. Study on the oligomerization of cyclopentadiene and
dicyclopentadiene to tricyclopentadiene through Diels-Alder reaction / Zhongqiang Xiong, Zhentao Mi,
Xiangwen Zhang // Reaction Kinetics and Catalysis Letters. – 2005. – Vol. 85. – P. 89–97. 4. Synthesis of
Cyclopentane from Dicyclopentadiene under Conditions of Concurrent Downward Flow in the Catalytic
Zone of a Reactive Distillation Units / A. Baiguzing, A. Burmistrov, A. Irdinkin, P. Filina, M. // Kataliz v
promyshlennosti. – 2018. – Vol. 18. – P. 6–12. 5. Copolymerization of cyclopentadiene with styrene by
methylaluminoxane catalyst / Hou J., Zhang D., Lin R., Zhang D., Wang S. and Sun W.-H. // Polym. Adv.
Technol. – 2006. – Vol. 17. – P. 486–490. 6. Bondaletov V. H. Yspolzovanye zhydkykh produktov pyrolyza
uhlevodorodnoho syria v synteze neftepolymernykh smol / V. H. Bondaletov, L. Y. Bondaletova, Nhuen Van
Tkhan // Uspekhy sovremennoho estestvoznanyia. – 2015. – No. 1(7) – S. 1130–113. 7. Dvostadiinyi sposib
initsiiovanoi koolihomeryzatsii nenasychenykh vuhlevodniv fraktsii S9 / O. M. Orobchuk, R. O. Subtelnyi,
Z. Iu. Maresh, B. O. Dziniak // Visnyk Natsionalnoho universytetu „Lvivska politekhnika” “Khimiia,
tekhnolohiia rechovyn ta yikh zastosuvannia”. – 2014. – No. 787. – S. 154–159. 8. Orobchuk O. M.
Vyvchennia vplyvu dozuvannia initsiatora na protses suspenziinoi koolihomeryzatsii vuhlevodnevoi fraktsii /
O. M. Orobchuk, R. O. Subtelnyi, B. O. Dziniak // Vostochno-Evropeiskyi zhurnal peredovykh tekhnolohyi
“Tekhnolohyy orhanycheskykh y neorhanycheskykh veshchestv”. – 2014. – No. 4/6 (70). – S. 14–18.