TY - JOUR
T1 - Synthesis and polymerization of renewable 1,3-cyclohexadiene using metathesis, isomerization, and cascade reactions with late-metal catalysts
AU - Mathers, Robert T.
AU - Shreve, Michael J.
AU - Meyler, Etan
AU - Damodaran, Krishnan
AU - Iwig, David F.
AU - Kelley, Diana J.
PY - 2011/9/1
Y1 - 2011/9/1
N2 - 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)(PPh 3) 3] ratios as high as 5 000. The isomerization and subsequent polymerization of the renewable 1,3-CHDwas 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.
AB - 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)(PPh 3) 3] ratios as high as 5 000. The isomerization and subsequent polymerization of the renewable 1,3-CHDwas 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.
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U2 - 10.1002/marc.201100104
DO - 10.1002/marc.201100104
M3 - Article
C2 - 21648003
AN - SCOPUS:82255171634
SN - 1022-1336
VL - 32
SP - 1338
EP - 1342
JO - Macromolecular Rapid Communications
JF - Macromolecular Rapid Communications
IS - 17
ER -