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Ring-Opening Metathesis Polymerization: History
Please note this is an old version of this entry, which may differ significantly from the current revision.
Subjects: Polymer Science
Contributor: Helena Kang

Ring-opening metathesis polymerization (ROMP) is a chain-growth polymerization in which a metal–alkylidene catalyst opens a cyclic olefin by olefin metathesis and incorporates the ring as a linear unsaturated repeat unit [1][2]. The concept is bounded by a cyclic olefin monomer, a metathesis-active alkylidene initiator, and a propagation step that is itself a metathesis event rather than an insertion into a metal–alkyl bond. Essential features are relief of ring strain as a thermodynamic driving force, a (2+2) cycloaddition–cycloreversion sequence at the metal–carbene, and retention of a double bond in each newly formed backbone linkage [1]. Living ROMP requires an initiator that enters the propagating state rapidly relative to chain growth and that suppresses chain transfer, so that molecular weight is set by the monomer-to-initiator ratio [2]. Macrocyclic monomers enable sequence-controlled ROMP by encoding a defined motif within each ring that is then unrolled into the chain [3]. Metal-free ROMP variants generate the metathesis-active species photochemically from an organic initiator, while enol-ether monomers furnish polymers that remain metathesis-derived yet contain hydrolytically labile linkages [4]. ROMP is distinguished from ring-opening polymerization of lactones or epoxides by the metathesis rather than nucleophilic or coordination-insertion mechanism, and from acyclic diene metathesis by the cyclic identity of the monomer.

  • ROMP
  • cyclic olefin
  • metal alkylidene
  • living metathesis

Synthetic Organic Chemistry Methods • Organic Chemistry • Chemistry • Physical Sciences

References

  1. Christopher W. Bielawski; Robert H. Grubbs; Highly Efficient Ring-Opening Metathesis Polymerization (ROMP) Using New Ruthenium Catalysts Containing N-Heterocyclic Carbene Ligands. null 2000, 39, 2903-2906, 10.1002/1521-3773(20000818)39:163.0.co;2-q.
  2. Tae‐Lim Choi; Robert H. Grubbs; Controlled Living Ring‐Opening‐Metathesis Polymerization by a Fast‐Initiating Ruthenium Catalyst. Angew. Chem. Int. Ed. 2003, 42, 1743-1746, 10.1002/anie.200250632.
  3. Will R. Gutekunst; Craig J. Hawker; A General Approach to Sequence-Controlled Polymers Using Macrocyclic Ring Opening Metathesis Polymerization. J. Am. Chem. Soc. 2015, 137, 8038-8041, 10.1021/jacs.5b04940.
  4. Kelli A. Ogawa; Adam E. Goetz; Andrew J. Boydston; Metal-Free Ring-Opening Metathesis Polymerization. J. Am. Chem. Soc. 2015, 137, 1400-1403, 10.1021/ja512073m.
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