Biobased Poly-phosphonate Additives from Methyl Linoleates

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.