title: Synthesis and polymerization of renewable 1,3-cyclohexadiene using metathesis, isomerization, and cascade reactions with late-metal catalysts.
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)(PPh3)3. The isomerization reaction was conducted for 1 h in neat 1,4-CHD with [1,4-CHD]/[RuHCl(CO)(PPh3)3] ratios as high as 5000. 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.
authors.affiliation: Department of Chemistry, Pennsylvania State University, New Kensington, Pennsylvania 15068, USA. rtm11@psu.edu.
authors.forename: Robert T
authors.initials: RT
authors.lastname: Mathers
authors.forename: Michael J
authors.initials: MJ
authors.lastname: Shreve
authors.forename: Etan
authors.initials: E
authors.lastname: Meyler
authors.forename: Krishnan
authors.initials: K
authors.lastname: Damodaran
authors.forename: David F
authors.initials: DF
authors.lastname: Iwig
authors.forename: Diana J
authors.initials: DJ
authors.lastname: Kelley
mesh_terms: D002384:Catalysis; D053138:Cyclohexenes / Q000138:chemical synthesis* / Q000737:chemistry; D055772:Green Chemistry Technology; D000077222:Limonene; D058105:Polymerization; D012428:Ruthenium / Q000737:chemistry; D013024:Soybean Oil / Q000737:chemistry*; D013237:Stereoisomerism; D013729:Terpenes / Q000737:chemistry; D014050:Toluene / Q000737:chemistry
chemical_list: D053138:Cyclohexenes; D013729:Terpenes; C048401:1,4-cyclohexadiene; D014050:Toluene; D012428:Ruthenium; D013024:Soybean Oil; D000077222:Limonene; C034005:1,3-cyclohexadiene