Biobased Poly-phosphonate Additives from Methyl Linoleates^‡

^‡Mention of trade names or commercial products in this publication is solely for the purpose of providing specific information and does not imply recommendation or endorsement by the U.S. Department of Agriculture. USDA is an equal opportunity provider and employer.

Abstract

Poly-dialkyl phosphonates were synthesized by reacting methyl linoleate with dimethyl, diethyl, and di-n-butyl phosphites in the presence of free radical initiator and positively identified and characterized using gas chromatography–mass spectrometry (GC-MS), nuclear magnetic resonance (NMR; ¹H, ¹³C, ³¹P), and Fourier transform infrared (FTIR). Neat poly-dialkyl phosphonates and their blends in high-oleic sunflower oil (HOSuO) and polyalphaolefin (PAO-6) base oils were investigated for their physical, chemical, and tribological properties. At room temperature, the poly-dialkyl phosphonates displayed much better solubility in HOSuO than in PAO-6. Solubility in the base oils increased in the order dimethyl < diethyl < di-n-butyl. Relative to methyl linoleate, the neat poly-dialkyl phosphonates displayed higher density, higher kinematic viscosity, higher oxidation stability, and better cold flow (lower pour point and cloud point) properties. As an additive (0–10% w/w) in HOSuO, increasing concentration of poly-di-n-butyl phosphonate resulted in increasing onset and peak oxidation temperatures and decreasing cloud point. Poly-di-n-butyl phosphonate blends in HOSuO also showed lower four-ball antiwear (AW) coefficient of friction (COF) and wear scar diameter (WSD) than corresponding blends with zinc dialkyl dithiophosphate (ZDDP). As an additive (0–10% w/w) in PAO-6 base oil, poly-di-n-butyl phosphonate displayed lower four-ball antiwear COF and comparable WSD relative to similar blends of ZDDP in PAO-6. The results indicate that poly-dialkyl phosphonates are promising biobased AW additives with comparable or better performance than current petroleum-based commercial AW additives such as ZDDP.

Keywords:

• Four-ball tribometer
• biobased additives
• biobased antiwear additives
• coefficient of friction (COF)
• high-oleic sunflower oil (HOSuO)
• methyl linoleate
• polyalphaolefin (PAO-6)
• poly-dialkyl phosphonates
• poly-di-n-butyl phosphonate
• wear scar diameter (WSD)
• dialkyl phosphites
• zinc dialkyl dithiophosphate (ZDDP)

Acknowledgements

The authors are grateful to the Elco Corporation for providing free sample of ZDDP and to Ineos Oligomers for providing free samples of PAO-6. The authors thank Linda Manthey and Linda Cao for their technical help.