Living Carbocationic Polymerization of Styrene in the Presence of Proton Trap

Living Cationic Polymerization of Styrene with TiCl3(OiPr) as a Lewis Acid Activator

“…2 Such a view on the living cationic polymerization of styrene, however, has been changing, in accordance with the developments of living processes for other vinyl monomers with electron-donating substituents like vinyl ethers. [8][9][10][11] However, the MWDs with the TiCl 4 -based initiating systems were broader (M h w /M h n ∼ 1.8) than those with the SnCl 4 -based counterparts. 4,5 The initiating system of choice consists of the HCl adduct of styrene [1, 1-phenylethyl chloride, CH 3 CH(Ph)Cl] as an initiator, and in the presence of tetra-n-butylammonium chloride (nBu 4 N + Cl -) it affords polystyrenes with narrow MWDs (M h w /M h n ∼ 1.1) and molecular weights controlled by the monomer/initiator mole ratio.…”

Facile synthesis of diphenylethylene end-functional polyisobutylene and its applications for the synthesis of block copolymers containing poly(methacrylate)s

“…2-Chloro-2,4,4-trimethylpentane (TMPCl) and 5-tert-butyl-1,3-bis(1-chloro-1-methylethyl)benzene ( t BuDiCumCl) were synthesized according to the literature [14,15]. PDDPE was prepared by using procedures analogous to those reported by Tung and Lo [16].…”

Star and Hyperbranched Polyisobutylenes via Terminally Reactive Polyisobutylene‐Polystyrene Block Copolymers

“…Due to these special properties, several attempts have been reported on the synthesis of highly branched polyisobutylenes so far 12–16, 20–33. Previously, it was found that intra‐ and intermolecular Friedel‐Crafts alkylation of the benzene rings of styrene (St) units in polystyrene (PSt) segments might occur by carbocationic chain ends 13, 16–23, 34, 35. This undesired side reaction was observed not only during the cationic polymerization of pure St,35 but in the case of the preparation of thermoplastic elastomer block copolymers composed of PIB and PSt13–19 as well.…”

“…Previously, it was found that intra‐ and intermolecular Friedel‐Crafts alkylation of the benzene rings of styrene (St) units in polystyrene (PSt) segments might occur by carbocationic chain ends 13, 16–23, 34, 35. This undesired side reaction was observed not only during the cationic polymerization of pure St,35 but in the case of the preparation of thermoplastic elastomer block copolymers composed of PIB and PSt13–19 as well. The goal of this work was to utilize this, otherwise unwanted side reaction for the synthesis of star and hyperbranched PIBs based on monofunctional polyisobutylene‐ block ‐polystyrene (PIB‐ b ‐PSt) and bifunctional polystyrene‐ block ‐polyisobutylene‐ block ‐polystyrene (PSt‐ b ‐PIB‐ b ‐PSt) copolymers, respectively.…”