We report on the synthesis, characterisation, and physical and tribological properties of halogen-free ionic liquids based on various chelated orthoborate anions with different phosphonium cations, both without halogen atoms in their structure. Important physical properties of the ILs including glass transition temperatures, density, viscosity and ionic conductivity were measured and are reported here. All of these new halogen-free orthoborate ionic liquids (hf-BILs) are hydrophobic and hydrolytically stable liquids at room temperature. As lubricants, these hf-BILs exhibit considerably better antiwear and friction reducing properties under boundary lubrication conditions for steel–aluminium contacts as compared with fully formulated (15W-50 grade) engine oil. Being halogen free these hf-BILs offer a more environmentally benign alternative to ILs being currently developed for lubricant applications.

This work reports on the synthesis and physicochemical characterisation of novel halogen-free boron containing ionic liquids (hf-BILs) with dialkylpyrrolidinium cations [C_nC₁Pyrr]⁺, n = 4–14, and bis(mandelato)borate anion [BMB]⁻. All the synthesised compounds are liquids at room temperature. It was found that the thermal properties and density of these hf-BILs are affected by the length of the longest alkyl chain connected to the nitrogen atom in the pyrrolidinium cations. Differential scanning calorimetry measurements revealed that glass transition temperatures of these ionic liquids are in the temperature range from 218 to 241 K. Interestingly, the glass transition temperatures follow the “odd–even” effect related to the number of carbons (n) in one of the alkyl chains of [C_nC₁Pyrr]⁺. It was also found that hf-BILs' density decreases with an increase in the alkyl chain length of [C_nC₁Pyrr]⁺. It is suggested that the “odd–even” effect is associated with the difference in packing and specific interactions of cations and anions of this class of hf-BILs. Their lubricating properties, as 3 wt% additives in polyethylene glycol (PEG), were evaluated in steel–steel contacts. PEG with hf-BILs additive provided significantly lower wear and friction compared to the neat PEG and 5W40 engine oil. It was found that shortening the length of the longest alkyl chain in the cations of [C_nC₁Pyrr][BMB] significantly reduces frictional losses. Antiwear properties of [C_nC₁Pyrr][BMB] in PEG follow the same trend.