Chemistry:Ring-opening metathesis polymerization

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Short description: Type of chain-growth polymerisation reaction involving cyclic olefins

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In polymer chemistry, ring-opening metathesis polymerization (ROMP) is a type of chain-growth polymerization involving olefin metathesis.[1] The reaction is driven by relieving ring strain in cyclic olefins.[2] A variety of heterogeneous and homogeneous catalysts have been developed for different polymers and mechanisms.[3] Heterogeneous catalysts are typical in large-scale commercial processes, while homogeneous catalysts are used in finer laboratory chemical syntheses.[4] Organometallic catalysts used in ROMP usually have transition metal centres, such as tungsten, ruthenium, titanium, etc., with organic ligands.[5]

Heterogeneous catalysis

ROMP reaction giving polynorbornene. Like most commercial alkene metathesis processes, this reaction does not employ a well-defined molecular catalyst.

Heterogeneous catalysis consists of catalysts and substrates in different physical states. The catalyst is typically in solid phase.[6] The mechanism of heterogeneous ring-opening metathesis polymerization is still under investigation.[7]

Ring-opening metathesis polymerization of cyclic olefins has been commercialized since the 1970s.[4] Examples of polymers produced on an industrial level through ROMP catalysis are Vestenamer, Norsorex and ZEONEX, among others.[8]

Mechanism

The mechanism of homogeneous ring-opening metathesis polymerization is well-studied. It is similar to any olefin metathesis reaction. Initiation occurs by forming an open coordination site on the catalyst. Propagation happens via a metallacycle intermediate formed after a 2+2 cycloaddition. When using a G3 catalyst, 2+2 cycloaddition is the rate determining step.[9]

Frontal ring-opening metathesis polymerization

Frontal ring-opening metathesis polymerization (FROMP) is a variation of ROMP. It is a polymerization system that reacts via a cascading reaction front after application of a trigger to kick off the reaction in a localized zone.[10] One example of this system is the FROMP of dicyclopentadiene with a Grubbs' catalyst initiated by heat.[11]

See also

Further reading

References

  1. ↑ Buchmeiser, Michael R. (2009-01-28), Dubois, Philippe; Coulembier, Olivier; Raquez, Jean-Marie, eds., "Ring-Opening Metathesis Polymerization" (in en), Handbook of Ring-Opening Polymerization (Wiley): pp. 197–225, doi:10.1002/9783527628407.ch8, ISBN 978-3-527-31953-4, https://onlinelibrary.wiley.com/doi/10.1002/9783527628407.ch8, retrieved 2024-12-02 
  2. ↑ Duda, Andrzej; Kowalski, Adam (2009-01-28), Dubois, Philippe; Coulembier, Olivier; Raquez, Jean-Marie, eds., "Thermodynamics and Kinetics of Ring-Opening Polymerization" (in en), Handbook of Ring-Opening Polymerization (Wiley): pp. 1–51, doi:10.1002/9783527628407.ch1, ISBN 978-3-527-31953-4, https://onlinelibrary.wiley.com/doi/10.1002/9783527628407.ch1, retrieved 2024-12-02 
  3. ↑ Hilf, Stefan; Kilbinger, Andreas F. M. (2009-09-23). "Functional end groups for polymers prepared using ring-opening metathesis polymerization" (in en). Nature Chemistry 1 (7): 537–546. doi:10.1038/nchem.347. ISSN 1755-4330. PMID 21378934. Bibcode: 2009NatCh...1..537H. https://www.nature.com/articles/nchem.347. 
  4. ↑ 4.0 4.1 Kirk-Othmer, ed (2001-01-26) (in en). Kirk-Othmer Encyclopedia of Chemical Technology (1 ed.). Wiley. doi:10.1002/0471238961.metanoel.a01. ISBN 978-0-471-48494-3. https://onlinelibrary.wiley.com/doi/book/10.1002/0471238961. 
  5. ↑ Cowie, J. M. G.; Arrighi, V. (2008). Polymers: chemistry and physics of modern materials (3rd ed.). Boca Raton: CRC Press. ISBN 978-0-8493-9813-1. OCLC ocm82473191. https://www.worldcat.org/title/ocm82473191. 
  6. ↑ Ehrhorn, Henrike; Tamm, Matthias (March 2019). "Well-Defined Alkyne Metathesis Catalysts: Developments and Recent Applications" (in en). Chemistry – A European Journal 25 (13): 3190–3208. doi:10.1002/chem.201804511. ISSN 0947-6539. PMID 30346054. https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/chem.201804511. 
  7. ↑ Greenlee, Andrew J.; Weitekamp, Raymond A.; Foster, Jeffrey C.; Leguizamon, Samuel C. (2024-04-19). "PhotoROMP: The Future Is Bright" (in en). ACS Catalysis 14 (8): 6217–6227. doi:10.1021/acscatal.4c00972. ISSN 2155-5435. PMID 38660608. 
  8. ↑ Mol, J. C. (2004-04-13). "Industrial applications of olefin metathesis". Journal of Molecular Catalysis A: Chemical. The 15th. International Symposium on Olefin Metathesis and Related Chemistry 213 (1): 39–45. doi:10.1016/j.molcata.2003.10.049. ISSN 1381-1169. https://linkinghub.elsevier.com/retrieve/pii/S1381116903007830. 
  9. ↑ Hyatt, Michael G.; Walsh, Dylan J.; Lord, Richard L.; Andino Martinez, José G.; Guironnet, Damien (2019-11-06). "Mechanistic and Kinetic Studies of the Ring Opening Metathesis Polymerization of Norbornenyl Monomers by a Grubbs Third Generation Catalyst" (in en). Journal of the American Chemical Society 141 (44): 17918–17925. doi:10.1021/jacs.9b09752. ISSN 0002-7863. https://pubs.acs.org/doi/10.1021/jacs.9b09752. 
  10. ↑ Pojman, J.A. (2012), "Frontal Polymerization" (in en), Polymer Science: A Comprehensive Reference (Elsevier): pp. 957–980, doi:10.1016/b978-0-444-53349-4.00124-2, ISBN 978-0-08-087862-1, https://linkinghub.elsevier.com/retrieve/pii/B9780444533494001242, retrieved 2024-12-02 
  11. ↑ Moneypenny, Timothy P.; Liu, Huiying; Yang, Anna; Robertson, Ian D.; Moore, Jeffrey S. (2017-04-13). "Grubbs-inspired metathesis in the Moore group" (in en). Journal of Polymer Science Part A: Polymer Chemistry 55 (18): 2935–2948. doi:10.1002/pola.28592. ISSN 0887-624X. Bibcode: 2017JPoSA..55.2935M. 



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