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Synthesis and Polymerization of Renewable 1,3‐Cyclohexadiene Using Metathesis, Isomerization, and Cascade Reactions with Late‐metal Catalysts
Author(s) -
Mathers Robert T.,
Shreve Michael J.,
Meyler Etan,
Damodaran Krishnan,
Iwig David F.,
Kelley Diana J.
Publication year - 2011
Publication title -
macromolecular rapid communications
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.348
H-Index - 154
eISSN - 1521-3927
pISSN - 1022-1336
DOI - 10.1002/marc.201100104
Subject(s) - isomerization , polymerization , metathesis , catalysis , ring opening metathesis polymerisation , chemistry , salt metathesis reaction , ruthenium , organic chemistry , polymer chemistry , polymer
Abstract Synthesis and subsequent polymerization of renewable 1,3‐cyclohexadiene (1,3‐CHD) from plant oils is reported via metathesis and isomerization reactions. The metathesis reaction required no plant oil purification, minimal catalyst loading, no organic solvents, and simple product recovery by distillation. After treating soybean oil with a ruthenium metathesis catalyst, the resulting 1,4‐cyclohexadiene (1,4‐CHD) was isomerized with RuHCl(CO)(PPh 3 ) 3 . The isomerization reaction was conducted for 1 h in neat 1,4‐CHD with [1,4–CHD]/[RuHCl(CO)(PPh 3 ) 3 ] ratios as high as 5 000. The isomerization and subsequent polymerization of the renewable 1,3‐CHD was examined as a two‐step sequence and as a one‐step cascade reaction. The polymerization was catalyzed with nickel(II)acetylacetonate/methaluminoxane in neat monomer, hydrogenated d ‐limonene, and toluene. The resulting polymers were characterized by FTIR, DSC, and TGA.