Submitted to: Chemical Engineering Communications
Publication Type: Peer Reviewed Journal
Publication Acceptance Date: 11/17/2015
Publication Date: 4/1/2016
Publication URL: http://handle.nal.usda.gov/10113/62499
Citation: Doll, K.M., Walter, E.L., Bantchev, G.B., Jackson, M.A., Murray, R.E., Rich, J.O. 2016. Improvement of lubricant materials using ruthenium isomerization. Chemical Engineering Communications. 203(7):901-907.
Interpretive Summary: Finding a replacement for petroleum is a difficult process. The desire to find a lubricant that can be made from vegetable oils is an especially high profile, yet possible, project. The compatibility of lubricant additives currently on the market with vegetable oil based lubricants is a problem that has been partially solved by using other vegetable oil based materials to make effective additives. One of those materials is called 9(10)-dibutyl phosphono stearate. It has been made through a chemical process by an ARS scientist. Now, in this work, combining the synthesis with another ARS technology, our new process creates not just one, but an entire series of new chemical compounds. In a second part of this work, this same technology is used to make synthetic motor oil components. Overall, these are a couple of steps on the road to valuable industrial materials from agriculture.
Technical Abstract: Production of an effective industrial lubricant additive from vegetable oils is a high profile and difficult undertaking. One candidate is alkyl 9(10)-dibutylphosphonostearate, which has been made through a radical transformation of alkyl 9-cis-octadecanoate. It is effective, but still suffers from drawbacks. In this report, synethsis is combined with a ruthenium based isomerization process to create not just one, but an entire series of new chemical compounds. A low level of [Ru(CO)2(EtCO2)]n is first used for the isomerization of the starting material, then radical chemistry is employed. A series of methyl dibutylphosphonooctadecanoates was made. In an analogous fashion, trans-7-tetradecene was also isomerized and then polymerized. As in the phosphonate case, the follow-up chemistry could be performed in the presence of the residual isomerization catalyst. The alkane:alkene ratio, observed by 1H NMR, was found to change from 14:1 in the isomerized starting material to a value of 41:1 in the polymerized material. This methodology, isomerization in tandem with other reactions, gives suitable routes to both biobased polyolefins, and biobased phosphonates, potential key ingredients in biobased lubrication formulations.