Ring-opening metathesis polymerization

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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

File:Polynbornene.png
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

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References

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