One-Pot Double Modification of p(NIPAAm): A Tool for Designing Tailor-Made Multiresponsive Polymers.

A quantitative, additive-free, and one-pot reaction cascade involving the ring-opening of a thiolactone by primary amine treatment and subsequent conversion of the released thiol groups via Michael addition to an acrylate has been utilized for the double modification/functionalization of poly(-isopropyl acrylamide), yielding tailor-made thermoresponsive polymers. After proving a quantitative double functionalization, different amine/acrylate combinations were employed in order to demonstrate the general applicability of the concept. Cloud points can be tuned by adjusting the amount of ring-opening amine in the reaction mixture, which enables to control the degree of modification.

From NMP to RAFT and thiol-ene chemistry by in situ functionalization of nitroxide chain ends.

A straightforward, novel strategy based on the in situ functionalization of polymers prepared by nitroxide-mediated polymerization (NMP), for the use as an extension toward block copolymers and post-polymerization modifications, has been investigated. The nitroxide end group is exchanged for a thiocarbonylthio end group by a rapid transfer reaction with bis(thiobenzoyl) disulfide to generate in situ reversible addition-fragmentation chain transfer (RAFT) macroinitiators. Moreover, not only have these macroinitiators been used in chain extension and block copolymerization experiments by the RAFT process but also a thiol-terminated polymer is synthesized by aminolysis of the RAFT end group and subsequently reacted with dodecyl vinyl ether by thiol-ene chemistry.