Issue 23, 2019

Integration of metal-free ring-opening metathesis polymerization and organocatalyzed ring-opening polymerization through a bifunctional initiator

Abstract

We have investigated the use of metal-free ring-opening metathesis polymerization (MF-ROMP) in combination with organocatalyzed ring-opening polymerization (o-ROP) to produce diblock copolymers with highly disparate block compositions via exclusively metal-free methods. Use of a bifunctional initiator bearing a vinyl ether as organic initiator for MF-ROMP and an alcohol for initiation of o-ROP allowed for investigation of three synthetic approaches: (1) sequential polymerization with isolation of the intermediate macroinitiators, (2) simultaneous bidirectional polymerizations, and (3) “one-pot” sequential monomer addition. Macroinitiators formed by first conducting o-ROP were successfully used in subsequent MF-ROMP to prepare diblock copolymers. Simultaneous MF-ROMP and o-ROP was thwarted by incompatible cross-combinations of catalysts and monomers. Finally, a straightforward “one-pot” synthesis of block copolymers, using o-ROP followed by MF-ROMP, was realized by sequential addition of each monomer-catalyst combination.

Graphical abstract: Integration of metal-free ring-opening metathesis polymerization and organocatalyzed ring-opening polymerization through a bifunctional initiator

Supplementary files

Article information

Article type
Communication
Submitted
02 okt 2018
Accepted
08 nov 2018
First published
08 nov 2018

Polym. Chem., 2019,10, 2975-2979

Author version available

Integration of metal-free ring-opening metathesis polymerization and organocatalyzed ring-opening polymerization through a bifunctional initiator

P. Lu and A. J. Boydston, Polym. Chem., 2019, 10, 2975 DOI: 10.1039/C8PY01417E

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