A straightforward procedure to α,ω-thiol telechelics was analyzed on the basis of reversible addition fragmentation chain transfer (RAFT) polymerization. It was observed that this technique allows α,ω- thiol functionalized polymers to be prepared directly from a difunctional chain transfer agent with only one postpolymerization reaction. The dithioester termini were converted to thiols by way of aminolysis in the presence of an antioxidant to yield the difunctional polymers with narrow molecular weight distributions. The α,ω-thiol telechelics showed greatly improved thermal properties in the absence of the dithioester end group.
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