Type of chain-growth polymerisation reaction involving cyclic olefins
Inpolymer chemistry ,ring-opening metathesis polymerization (ROMP ) is a type ofchain-growth polymerization involvingolefin metathesis .[ 1] ring strain in cyclicolefins .[ 2] heterogeneous andhomogeneous catalysts have been developed for different polymers and mechanisms.[ 3] [ 4] Organometallic catalysts used in ROMP usually havetransition metal centres, such as tungsten, ruthenium, titanium, etc., with organicligands .[ 5]
Heterogeneous catalysis [ edit ] ROMP reaction givingpolynorbornene . 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] [ 7]
Ring-opening metathesis polymerization of cyclic olefins has been commercialized since the 1970s.[ 4] [ 8]
The mechanism of homogeneous ring-opening metathesis polymerization is well-studied. It is similar to anyolefin metathesis reaction. Initiation occurs by forming an open coordination site on the catalyst. Propagation happens via ametallacycle 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 [ edit ] 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] dicyclopentadiene with aGrubbs' catalyst initiated by heat.[ 11]
Bano, Tahira; Zahoor, Ameer Fawad; Rasool, Nasir; Irfan, Muhammad; Mansha, Asim (June 2022)."Recent trends in Grubbs catalysis toward the synthesis of natural products: a review" Journal of the Iranian Chemical Society .19 (6):2131– 2170.doi :10.1007/s13738-021-02463-x .ISSN 1735-207X . Sveinbjörnsson, Benjamin R.; Weitekamp, Raymond A.; Miyake, Garret M.; Xia, Yan; Atwater, Harry A.; Grubbs, Robert H. (2012-09-04)."Rapid self-assembly of brush block copolymers to photonic crystals" .Proceedings of the National Academy of Sciences .109 (36):14332– 14336.Bibcode :2012PNAS..10914332S .doi :10.1073/pnas.1213055109 PMC 3437898 PMID 22912408 . ^ Buchmeiser, Michael R. (2009-01-28), Dubois, Philippe; Coulembier, Olivier; Raquez, Jean-Marie (eds.),"Ring-Opening Metathesis Polymerization" Handbook of Ring-Opening Polymerization (1 ed.), Wiley, pp. 197– 225,doi :10.1002/9783527628407.ch8 ,ISBN 978-3-527-31953-4 , retrieved2024-12-02 {{citation }}: CS1 maint: work parameter with ISBN (link )^ Duda, Andrzej; Kowalski, Adam (2009-01-28), Dubois, Philippe; Coulembier, Olivier; Raquez, Jean-Marie (eds.),"Thermodynamics and Kinetics of Ring-Opening Polymerization" Handbook of Ring-Opening Polymerization (1 ed.), Wiley, pp. 1– 51,doi :10.1002/9783527628407.ch1 ,ISBN 978-3-527-31953-4 , retrieved2024-12-02 {{citation }}: CS1 maint: work parameter with ISBN (link )^ Hilf, Stefan; Kilbinger, Andreas F. M. (2009-09-23)."Functional end groups for polymers prepared using ring-opening metathesis polymerization" Nature Chemistry .1 (7):537– 546.Bibcode :2009NatCh...1..537H .doi :10.1038/nchem.347 .ISSN 1755-4330 .PMID 21378934 . ^a b Kirk-Othmer, ed. (2001-01-26).Kirk-Othmer Encyclopedia of Chemical Technology doi :10.1002/0471238961.metanoel.a01 .ISBN 978-0-471-48494-3 ^ Cowie, J. M. G.; Arrighi, V. (2008).Polymers: chemistry and physics of modern materials ISBN 978-0-8493-9813-1 OCLC 82473191 . ^ Ehrhorn, Henrike; Tamm, Matthias (March 2019)."Well-Defined Alkyne Metathesis Catalysts: Developments and Recent Applications" Chemistry – A European Journal .25 (13):3190– 3208.doi :10.1002/chem.201804511 .ISSN 0947-6539 .PMID 30346054 . ^ Greenlee, Andrew J.; Weitekamp, Raymond A.; Foster, Jeffrey C.; Leguizamon, Samuel C. (2024-04-19)."PhotoROMP: The Future Is Bright" .ACS Catalysis .14 (8):6217– 6227.doi :10.1021/acscatal.4c00972 .ISSN 2155-5435 .PMC 11036397 PMID 38660608 . ^ 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 . ^ 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" Journal of the American Chemical Society .141 (44):17918– 17925.doi :10.1021/jacs.9b09752 .ISSN 0002-7863 . ^ Pojman, J.A. (2012),"Frontal Polymerization" 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 , retrieved2024-12-02 {{citation }}: CS1 maint: work parameter with ISBN (link )^ Moneypenny, Timothy P.; Liu, Huiying; Yang, Anna; Robertson, Ian D.; Moore, Jeffrey S. (2017-04-13)."Grubbs-inspired metathesis in the Moore group" .Journal of Polymer Science Part A: Polymer Chemistry .55 (18):2935– 2948.Bibcode :2017JPoSA..55.2935M .doi :10.1002/pola.28592 ISSN 0887-624X . 
