Cationic polymerization of dienes III. Polymerization of 1,3-pentadiene initiated by ferric chloride in hexane

New stage in living cationic polymerization: An array of effective Lewis acid catalysts and fast living polymerization in seconds

“…49 Despite these favorable features, FeCl 3 has never been used for living cationic polymerization, although there have been several examples of its use in the cationic polymerization of vinyl ethers, 50 styrenes, 51 and dienes. 52 The cationic polymerization of IBVE with IBVEHCl/FeCl 3 in toluene in the presence of 1,4-dioxane at 0 8C was complete in 15 s (Fig. 3), and a polymer with a very narrow MWD was obtained (M w /M n ¼ 1.06).…”

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

“…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 .…”

Fast living cationic polymerization of vinyl ethers with iron(III) chloride in the presence of a cyclic ether: Most active and environmentally benign catalyst for the living cationic polymerization of vinyl ethers

“…Although there are several examples of cati-onic polymerization of vinyl ethers, 15 styrenes, 16 and dienes 17 with FeCl 3 , living cationic polymerization has not been reported. 18 Here we report the living cationic polymerization of an alkyl vinyl ether with an FeCl 3 /cyclic ether initiating system.…”