Cationic polymerization of olefins using green acids

A process for cationically polymerizing olefin monomers in a controlled manner in a reaction mixture, the cationic polymerization process comprising:

• contacting olefin monomers and a catalytically effective amount of an initiating composition containing (A) a recyclable coinitiator, (B) a solubilizing agent, (C) an initiator, and optionally, (D) a nucleophilic additive, to form a reaction medium;
• wherein the recyclable coinitiator (A) is selected from aluminum, gallium, and
• indium perfluorinated organosulfonates of the formula (I):
• wherein M is a metal selected from aluminum, gallium, and indium, and R1, R2, and R3 are the same or different, and are selected from the group consisting of perfluoroalkylsulfonate or perfluoroarylsulfonate;
• wherein the solubilizing agent (B) is any compound soluble in the reaction medium that contains an n-donor atom and allows the recyclable coinitiator to induce controlled polymerization;
• wherein the initiator (C) is a compound selected from the group consisting of (i) carbocation synthons having the formula (II):
• wherein R4 is selected from an alkyl group, an aromatic group, and combinations thereof, wherein R5, and R6 are the same or different and are selected from an alkyl group, an aromatic group, an H, and combinations thereof, wherein n is an integer greater than or equal to 1 and is the number of initiator sites, and wherein X is selected from the group consisting of a functional group that the Lewis acid coinitiator abstracts to form an initiating carbocation, halogenium ion synthons, Brønsted acids, and silicenium ion synthons having the formula (III):
• wherein R7, R8, and R9 are the same or different and are selected from an alkyl group, an aromatic group, and combinations thereof, wherein n is an integer greater than or equal to 1 and is the number of initiator sites, and wherein X is the functional group that the Lewis acid coinitiator abstracts to form an initiating silicenium ion;
• and
• wherein the optional nucleophilic additive (D) is any compound that assists in controlling polymerization as allowed by the solubilizing agent, either by decreasing the ionicity of the system, or by stabilizing the propagating carbocation, or through increasing the anion nucleophilicity.