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Acyclic diene metathesis (ADMET) polymerization using a well‐defined ruthenium based metathesis catalyst
Author(s) -
Brzezinska Krystyna,
Wolfe Patrick S.,
Watson Mark D.,
Wagener Kenneth B.
Publication year - 1996
Publication title -
macromolecular chemistry and physics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.57
H-Index - 112
eISSN - 1521-3935
pISSN - 1022-1352
DOI - 10.1002/macp.1996.021970622
Subject(s) - acyclic diene metathesis , metathesis , chemistry , ruthenium , monomer , polymerization , diene , polymer chemistry , catalysis , reactivity (psychology) , polymer , ether , grubbs' catalyst , intramolecular force , ring opening metathesis polymerisation , medicinal chemistry , organic chemistry , medicine , natural rubber , alternative medicine , pathology
A series of α,ω‐dienes have been exposed to Ru(Cl 2 )(CHPh)(PCy 3 ) 2 , [Ru] 3 , metathesis catalyst under acyclic diene metathesis (ADMET) conditions, and the products were compared with those obtained previously using Schrock's well defined Mo and W alkylidenes. High molecular weight polymers can be synthesized using [Ru] 3 if lower monomer to catalyst ratios with respect to [Mo] 1 and [W] 2 are used. Monomer structure plays a role since 1,9‐decadiene produces molecular weights typical of ADMET chemistry, whereas 1,5‐hexadiene produces only oligomers. This decrease in reactivity is attributed to a manifestation of intramolecular π‐complexation of the tethered olefin in 1,5‐hexadiene polymerizations. Substituents at the 2‐position of α,ω‐dienes also affects polymerization in that only dimers can be produced from 2‐methyl‐1,5‐hexadiene, a result similar to the same reaction performed with [W] 2 . Diallyl ether oligomerizes effectively in the presence of [Ru] 3 with a ratio of cyclics to oligomers comparable to results obtained with [Mo] 1 and [W] 2 .