Oligomerization of piperylene and piperylene fraction in the presence of complex catalysts based on aluminium chloride

A New Insight into the Mechanism of 1,3‐Dienes Cationic Polymerization I: Polymerization of 1,3‐Pentadiene with tBuCl/TiCl4 Initiating System: Kinetic and Mechanistic Study

“…Moreover, the increase of polymerization rate with a lowering of the temperature is observed for all t BuCl/TiCl 4 ratios studied in this work (Figure S2, Supporting Information). Such behavior of the t BuCl/TiCl 4 initiating system in the polymerization of 1,3‐pentadiene is unique, since the strong decrease of the reaction rate with lowering of the temperature is observed for all known catalytic systems of 1,3‐diene polymerization . However, for cationic and especially controlled (or better quasiliving) cationic polymerization of vinyl monomers, the rate of polymerization is generally increased with the lowering of the temperature.…”

“…It is known that the cationic polymerization of 1,3‐pentadiene is co‐initiated by a wide range of Lewis acids such as AlCl 3 , FeCl 3 , SnCl 4 , BF 3 OEt 2 , VOCl 3 , and TiCl 4 . The main feature of TiCl 4 ‐based initiating systems is their low activity in the polymerization of 1,3‐dienes in the absence of purposely added initiators such as water, hydrochloric acid, organic acids, and so on, while the addition to the system of protic compounds or cationogens allowed to increase the rate of polymerization of 1,3‐dienes significantly .…”

“…The TiCl 4 ‐co‐initiated cationic polymerization of 1,3‐dienes in conjunction with water, acetone, trichloroacetic acid, trifluoroacetic acid, tert ‐butyl esters of these acids, cumyl acetate, cumyl methyl ether, dimethylallyl bromide, and dimethylallyl alcohol has been investigated. The obtained poly(1,3‐diene)s are characterized by reduced unsaturation that was explained either by intramolecular cyclization or branching due to the chain transfer to polymer . The unsaturated part of the polymer chain consists mainly of trans ‐1,4‐structures …”

Cationic polymerization of 1,3‐pentadiene coinitiated by zinc halides

“…). The formation of HMWF and IF is observed during the cationic polymerization of 1,3‐pentadiene using the initiating systems based on AlCl 3 ,7–15 FeCl 3 ,16 SnCl 4 ,17 TiCl 4 ,1–6,18–20 and VOCl 3 21. Depending on the nature of Lewis acid used, the appearance of HMWF and IF is revealed at the different stages of the polymerization process.…”