One-Pot Automated Synthesis of Quasi Triblock Copolymers for Self-Healing Physically Crosslinked Hydrogels.

The preparation of physically crosslinked hydrogels from quasi ABA-triblock copolymers with a water-soluble middle block and hydrophobic end groups is reported. The hydrophilic monomer N-acryloylmorpholine is copolymerized with hydrophobic isobornyl acrylate via a one-pot sequential monomer addition through reversible addition fragmentation chain-transfer (RAFT) polymerization in an automated parallel synthesizer, allowing systematic variation of polymer chain length and hydrophobic-hydrophilic ratio. Hydrophobic interactions between the outer blocks cause them to phase-separate into larger hydrophobic domains in water, forming physical crosslinks between the polymers.

Double Modification of Polymer End Groups through Thiolactone Chemistry.

A straightforward synthetic procedure for the double modification and polymer-polymer conjugation of telechelic polymers is performed through amine-thiol-ene conjugation. Thiolactone end-functionalized polymers are prepared via two different methods, through controlled radical polymerization of a thiolactone-containing initiator, or by modification of available end-functionalized polymers. Next, these different linear polymers are treated with a variety of amine/acrylate-combinations in a one-pot procedure, creating a library of tailored end-functionalized polymers.