Mathers Robert T, Shreve Michael J, Meyler Etan, Damodaran Krishnan, Iwig David F, Kelley Diana J
Department of Chemistry, Pennsylvania State University, New Kensington, Pennsylvania 15068, USA.
Macromol Rapid Commun. 2011 Sep 1;32(17):1338-42. doi: 10.1002/marc.201100104. Epub 2011 Jun 3.
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.
据报道，通过复分解和异构化反应可从植物油合成可再生的1,3 - 环己二烯（1,3-CHD）并随后进行聚合。复分解反应无需对植物油进行纯化，催化剂负载量极低，无需有机溶剂，且通过蒸馏即可简单地回收产物。用钌复分解催化剂处理大豆油后，所得的1,4 - 环己二烯（1,4-CHD）用RuHCl(CO)(PPh3)3进行异构化。异构化反应在纯1,4-CHD中进行1小时，[1,4-CHD]/[RuHCl(CO)(PPh3)3]比例高达5000。对可再生1,3-CHD的异构化及随后的聚合反应进行了两步法和一步级联反应研究。聚合反应在纯单体、氢化d - 柠檬烯和甲苯中用乙酰丙酮镍（II）/甲基铝氧烷催化。通过傅里叶变换红外光谱（FTIR）、差示扫描量热法（DSC）和热重分析法（TGA）对所得聚合物进行了表征。
