Quantitative preparation of allyl telechelic polyisobutylene under reflux conditions

A method for controlling the temperature for conducting living cationic polymerization of isobutylene above −78° C. comprising:

• A) providing an externally cooled reaction vessel;
• B) charging said externally cooled reaction vessel with isobutylene, an initiator, a refluxing solvent mixture, and a proton trap at a temperature below a boiling point for said refluxing solvent mixture, wherein said refluxing solvent mixture comprises a polar solvent and a nonpolar solvent;
• C) allowing the temperature of the externally cooled reaction vessel to increase to the boiling point of said refluxing solvent mixture causing the refluxing solvent mixture to reflux;
• D) inducing living cationic polymerization of the isobutylene by the addition of a co-initiator to said externally cooled reaction vessel to produce polyisobutylene polymer chains;
• wherein the temperature inside said externally cooled reaction vessel is maintained at or about said boiling point during said living cationic polymerization.

A method of making a di-telechelic allyl-functionalized polyisobutylene by living cationic polymerization of isobutylene comprising:

• A) providing an externally cooled reaction vessel equipped with a reflux condenser;
• B) charging said externally cooled reaction vessel with isobutylene, a bi-functional initiator, a refluxing solvent mixture comprising propane and methyl chloride, and a proton trap at a temperature below a boiling point for said refluxing solvent mixture;
• C) allowing the temperature of the externally cooled reaction vessel to increase to the boiling point of said refluxing solvent mixture causing the refluxing solvent mixture to reflux;
• D) inducing living cationic polymerization of the isobutylene by the addition of a co-initiator to said externally cooled reaction vessel to produce polyisobutylene polymer chains;
• E) allowing living cationic polymerization to continue until substantially all of the isobutylene has been reacted;
• F) terminating the living cationic polymerization reaction by adding a termination agent, wherein said termination agent terminates the living cationic polymerization reaction by reacting with said polyisobutylene chains to leave terminal allyl functional groups on said polyisobutylene chains to produce the di-telechelic allyl-functionalized polyisobutylene.