End-functionalized polymers by controlled free-radical polymerization process and polymers made therefrom

A process for forming a polymer having at least one functionalized end group, the process comprising the steps of:

• (a) heating a mixture of an activated di-iodine reagent, a free-radical initiator, and at least one polymerizable monomer to form a pre-polymer, the activated di-iodine reagent being of the formula:
• I—R—I
• where R contains at least one radical stabilizing group and has 1-50 carbon atoms, the iodine and the radical stabilizing group are attached to the same carbon atom in R, and the radical stabilizing group is selected from the group consisting of an aryl, alkene, ester, acid, amide, ketone, nitrite, halogen, isocyanate, nitro and amine;
• and
• (b) functionalizing the pre-polymer by reaction with a nucleophilic reagent.

A process for forming a polymer having at least one functionalized end group, the process comprising the steps of:

• (a) heating a mixture of an iodine reagent having at least one iodine end group, a free-radical initiator, and at least one polymerizable monomer, the molar ratio of the free-radical initiator to the iodine reagent being 10 to 0.001, the molar ratio of the monomer to the iodine reagent being 10 to 1000;
• and
• (b) converting the iodine end group to the functionalized end group by reaction with a nucleophilic reagent wherein said iodine regent is selected from a compound of the formulae:
• Z2—R—I or I—R—I
• where R contains at least one radical stabilizing group and has 1-50 carbon atoms, the iodine and the radical stabilizing group are attached to the same carbon atom in R, and the radical stabilizing group is selected from the group consisting of an aryl, alkene, ester, acid, amide, ketone, nitrile, halogen, isocyanate, nitro and amine, and Z2 is selected from —OR1, —N(R1)2, —SR1, —COOR1, —COOM, olefin of the type —CR1═C(R1)2, epoxide of the type
• —SO3M, —PO(OR1)2, —PO(R1)3, —P(R1)3, —N═C═O and —CR1═O, wherein R1 is equal to H or a group having 1-20 carbon atoms, R1 being the same or different for any Z2 having more than one R1, and wherein M is a metal ion.