Metathesis chemistry has been the subject of numerous books and review articles, but the vast majority of these sources focus on molecular synthesis or kinetic investigations, with significantly less focus on polymerizations. Two excellent overviews that highlight the promises of ring-opening metathesis polymerization (ROMP) chemistry come from Christian Slugovc – first in the 2004 “The Ring Opening Metathesis Polymerisation Toolbox”, and now the 2010 “The ROMP toolbox upgraded.” As the titles imply, these articles are organized by the reaction factors and techniques that have been used to control polymerization rate and architecture, comparing general methodologies across many different studies.
The 2004 entry outlines four tools used for controlling metathesis polymerizations:
- Catalyst kinetics
- Monomer chemistry
- Neat polymerization vs. solvent and additive effects
- Time-temperature dependence
The discussion of these tools and the effects they have on ROMP is itself an excellent primer on the art, but Slugovc then uses a general review of current ROMP publications to illustrate the usage of these tools. The original “Toolbox” reviewed ROMP developments in biologically-active polymers, solid-supported reagents, and electronic applications. “Toolbox Upgraded” includes an extensive look at metathesis polymer architectures (homopolymers, random- and alternating copolymers, block copolymers), as well as recent advances in ROMP telechelics, grafted polymers, and stereoselectivity. The recent update also adds new summaries of new solvent effect investigations and developments in renewable-resource monomers, before closing with reviews of liquid crystal polymers, porous polymers, surface modifications, and self-healing polymers.
Together, the two articles present ROMP technology as it currently exists in all its incarnations, and offer a framework to understand where it can go next.