Patent Application
20140011720
The present invention relates to anti-wear and friction-reducing lubricant components comprising selected ionic liquids as well as a lubricant comprising the lubricant component.
Improper lubrication may result in high friction and wear losses, which can in turn adversely affect the fuel economy, durability of engines, environment and human health. Developing new technological solutions, such as use of lightweight non-ferrous materials, less harmful fuels, controlled fuel combustion processes or more efficient exhaust gas after-treatment, are possible ways to reduce the economical and environmental impact of machines. The commercially available lubricants are yet not appropriate for lightweight non-ferrous materials.
Ionic liquids (ILs) are purely ionic, salt-like materials that are usually liquid at low temperatures (below 100° C.). Some IL have melting points below 0° C. ILs have already found their diverse applications as catalysts, liquid crystals, green solvents in organic synthesis, in separation of metal ions, electrochemistry, photochemistry, CO2 storage devices, etc. ILs have a number of attractive properties, such as negligible volatility, negligible flammability, high thermal and chemical stability, low melting point and controllable miscibility with organic compounds and base oils. Recently, it was found that ILs can act as versatile lubricants and lubricant components in base oils and greases for different sliding pairs, see e.g. U.S. Pat. No. 3,239,463; US Patent Application Publication 2010/0227783 A1; US Patent Application Publication 2010/0187481 A1; U.S. Pat. No. 7,754,664 B2, Jul. 13, 2010; US Patent Application Publication 2010/0105586 A1. Due to their molecular structure and charges, ILs can be readily adsorbed on the sliding surfaces in frictional pairs, forming a boundary tribofilm, which reduces both friction and wear at low and high loads.
The choice of cations has an impact on properties of ILs and often, but not always defines their stability. Functionality of ILs is, in general, controlled by a choice of both the cation and the anion. Different combinations of a broad variety of already known cations and anions lead to a theoretically possible number of 1018. Today only about 1000 ILs are described in the literature, and approximately 300 of them are commercially available. ILs with cations imidazolium, ammonium and phosphonium and halogen-containing anions, tetrafluoroborates and hexafluorophosphates, are the most commonly used in tribological studies. Alkylimidazolium tetrafluoroborates and hexafluorophosphates have shown promising lubricating properties as base oils for a variety of contacts. However, some ILs with halogen atoms in their structure, for example, with tetrafluoroborates or/and hexafluorophosphates, are very reactive that may increase a risk for tribocorrosion in ferrous and non-ferrous contacts.
Imidazolium and Other ILs with BF4 Anion:
A literature survey shows that most of the IL lubricants successfully employed during the past decade in various ferrous and non-ferrous tribological contacts are based on boron-based anion, tetrafluoroborate [BF4]−[Ye, C., Liu, W., Chen, Y., Yu, L.: Room-temperature ionic liquids: a novel versatile lubricant. Chem. Commun. 2244-2245 (2001). Liu, W., Ye, C., Gong, Q., Wang, H., Wang, P.: Tribological performance of room-temperature ionic liquids as lubricant. Tribol. Lett. 13 (2002) 81-85. Chen, Y. X., Ye, C. F., Wang, H. Z., Liu, W. M.: Tribological performance of an ionic liquid as a lubricant for steel/aluminium contacts. J. Synth. Lubri. 20 (2003) 217-225. Jimenez, A. E., Bermudez, M. D., Iglesias, P., Carrion, F. J., Martinez-Nicolas, G.: 1-N-alkyl-3-methylimidazolium ionic liquids as neat lubricants and lubricant components in steel aluminum contacts. Wear 260 (2006) 766-782. Yu, G., Zhou, F., Liu, W., Liang, Y., Yan, S.: Preparation of functional ionic liquids and tribological investigation of their ultra-thin films. Wear 260 (2006) 1076-1080.]
Zhang et al. have reported that nitrile-functionalized ILs with BF4− anion have considerably better tribological performance in steel-steel and steel-aluminium contacts than ILs with NTf2− and N(CN)2− anions [Q. Zhang, Z. Li, J. Zhang, S. Zhang, L. Zhu, J. Yang, X. Zhang, Y. J. Deng. Physicochemical properties of nitrile-functionalized ionic liquids. J. Phys. Chem. B, 2007, 111, 2864-2872.] It has been suggested that the BF anion has excellent tribological performance but unfortunately the detailed mechanism was not described.
A comparison of the film formation properties of imidazolium ILs based on BF4− and PF6− anions in rolling-sliding steel-steel contacts using mini-traction machine (MTM) revealed that BF4− anion develop thicker tribofilm and provides lower friction (μ=0.01) compared to PF6− (μ=0.03) [H. Arora, P. M. Cann. Lubricant film formation properties of alkyl imidazolium tetrafluoroborate and hexafluorophosphate ionic liquids. Tribol. Int. 43 (2010) 1908-19161 The same family of ILs in titanium-steel contacts has shown that BF4 anion-based IL fails above room temperature while PF6— anion-based IL perform better up to 200° C. [A. E. Jimenez, M. D. Bermudez. Ionic liquids as lubricants of titanium—steel contact. part 2: friction, wear and surface interactions at high temperature. Tribol. Lett. 37 (2010) 431-443.] In steel-aluminium contacts, phosphonium IL with BF4− anion showed superior tribological properties including friction-reducing, antiwear and load carrying capacity to conventional imidazolium IL based on PF6− anion [X. Liu, F. Zhou, Y. Liang, W. Liu. Tribological performance of phosphonium based ionic liquids for an aluminum-on-steel system and opinions on lubrication mechanism. Wear 261 (2006) 1174-1179.] Similarly, phosphonium IL with BF4− anion exhibited excellent tribological performance at 20° C. and 100° C. in steel-steel contacts as compared to imidazolium-PF6− and conventional high temperature lubricants such as X-1P and perfluoropolyether PFPE [L. Wenga, X. Liu, Y. Liang, Q. Xue. Effect of tetraalkylphosphonium based ionic liquids as lubricants on the tribological performance of a steel-on-steel system. Tribol. Lett. 26 (2007) 11-17.]
However, the sensitivity of [BF4]− anion to moisture make such ILs undesirable in tribological and other industrial applications. During the past few years, efforts have been made by researchers to design and synthesize hydrolytically stable halogen-free boron-based ILs with improved performance.
Pyrrolidinium ILs with Halogenated Anions:
The lubricating properties of pyrrolidinium ILs with [BF4]− anion are not reported yet. However, pyrrolidinium IL with other halogenated anions are reported in literature as excellent lubricants and lubricant components for various tribological applications. Recently, pyrrolidinium ILs with halogenated anions have shown excellent lubrication performance in microelectromechanical systems (MEMS) [J. J. Nainaparampil, K. C. Eapen, J. H. Sanders, A. A. Voevodin. Ionic-Liquid Lubrication of Sliding MEMS Contacts: Comparison of AFM Liquid Cell and Device-Level Tests. J. Microelectromechanical Systems 16 (2007) 836-843.]
1-Butyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate, as is known to possess promising lubricating properties in non-ferrous coatings interfaces such as TiN, CrN and DLC [R. Gonzalez, A. H. Battez, D. Blanco, J. L. Viesca, A. Fernandez-Gonzalez. Lubrication of TiN, CrN and DLC PVD coatings with 1-Butyl-1-Methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate. Tribol. Lett. 40 (2010) 269-277.]
Cholinium ILs with Halogenated Anions:
Choline is biological molecule in the form of phosphatidylcholine (liposome), a major constituent of synovial fluid surface active phospholipids, are natural additives for cartilage lubricants in human beings [G. Verberne, A. Schroeder, G. Halperin, Y. Barenholz, I. Etsion, Liposomes as potential biolubricant components for wear reduction in human synovial joints. Wear 268 (2010) 1037-1042.] These molecules are widely used in effective biolubricants for friction and wear reduction in human synovial joints [S. Sivan, A. Schroeder, G. Verberne, Y. Merkher, D. Diminsky, A. Priev, A. Maroudas, G. Halperin, D. Nitzan, I. Etsion, Y. Barenholz. Liposomes act as effective biolubricants for friction reduction in human synovial joints. Langmuir 26 (2010) 1107-1116.]
Cholinium ILs, choline chloride, has recently shown excellent friction reducing performance in steel-steel contacts comparable to fully formulated engine oil (SAE 5W30 grade) [S. D. A. Lawes, S. V. Hainsworth, P. Blake, K. S. Ryder, A. P. Abbott. Lubrication of steel/steel contacts by choline chloride ionic liquids. Tribol. Lett. 37 (2010) 103-110.] These ILs are believed as green lubricants and have been known to have excellent corrosion inhibition properties [C. Gabler, C. Tomastik, J. Brenner, L. Pisarova, N. Doerr, G. Allmaier. Corrosion properties of ammonium based ionic liquids evaluated by SEM-EDX, XPS and ICP-OES. Green Chem. 13 (2011) 2869-2877.]
US 2009/0163394 discloses a number of ionic liquids, for instance Methyl-n-butylbis(diethylamino)-phosphonium bis(oxalato)borate. It briefly mentions that lubrication oils as a general application for ionic liquids. One drawback of the compounds that are disclosed is that the direct P—N bonds in cations of described phosphonium based ionic liquids are sensitive to hydrolysis, which is critical in many important applications including most of commercial lubricants with unavoidable presence of traces of water. Compounds with P—N bonds are very sensitive to hydrolysis and may hydrolyze to produce reactive species. Therefore, phosphonium cations with one and more P—N chemical bonds will be prone to hydrolysis in the presence of traces of water in a lubricant. Stability of a lubricant placed in a contact with water is a very important technical characteristics.
The most widely studied ionic liquids in tribological applications usually contain tetrafluoroborate (BF4−) and hexafluorophosphate (PF6−) anions. Probably, the reason is that both boron and phosphorus atoms have excellent tribological properties under high pressure and elevated temperature in the interfaces. However, BF4− and PF6− anions have high polarity and absorb water in the system. These anions are very sensitive to moisture and may hydrolyze to produce hydrogen fluoride among other products. These products cause corrosion by various tribochemical reactions, which can damage the substrate in the mechanical system. In addition, halogen-containing ILs may release toxic and corrosive hydrogen halides to the surrounding environment.
One major drawback of ionic liquids, which are known for lubrication purpose is that the halogens make them undesired for instance from an environmental perspective. Further corrosion may be a problem for some currently used ionic liquids in particular for hydrophilic ionic liquids.
Therefore, the development of new hydrophobic and halogen-free anions containing ILs is highly desired.
It is an object of the present invention to obviate at least some of the disadvantages in the prior art and provide an improved lubricant component as well as a lubricant comprising the component.
In a first aspect there is provided a lubricant component characterized in that it comprises: a) at least one anion selected from the group consisting of a mandelato borate anion, a salicylato borate anion, an oxalato borate anion, a malonato borate anion, a succinato borate anion, a glutarato borate anion and an adipato borate anion, and b) at least one cation selected from the group consisting of a tetraalkylphosphonium cation, a choline cation, an imidazolium cation, a borronium cation and a pyrrolidinium cation, wherein said at least one cation has at least one alkyl group substituent with the general formula CnH2n+1, wherein 1≦n≦80.
In one embodiment 1≦n≦60.
In one embodiment the anion is selected from the group consisting of a bis(mandelato)borate anion, a bis(salicylato)borate anion, and a bis(malonato)borate anion, and wherein the cation is a tetraalkylphosphonium cation.
In one embodiment the anion is bis(oxalato)borate and wherein the cation is a tetraalkylphosphonium cation.
In one embodiment the anion is a bis(succinato)borate anion and wherein the cation is a tetraalkylphosphonium cation.
In one embodiment the anion is selected from the group consisting of a bis(glutarato)borate anion and a bis(adipato)borate anion and wherein the cation is a tetraalkylphosphonium cation.
In one embodiment the only cation is tetraalkylphosphonium with the general formula PR′R3+, wherein R′ and R are CnH2n+1.
In one embodiment R′ is selected from the group consisting of C8H17 and C14H29, and wherein R is selected from the group consisting of C4H9 and C6H13.
In one embodiment the lubricant component comprises at least one selected from the group consisting of tributyloctylphosphonium bis(mandelato)borate; tributyltetradecylphosphonium bis(mandelato)borate; trihexyltetradecylphosphonium bis(mandelato)borate, tributyloctylphosphonium bis(salicylato)borate, tributyltetradecylphosphonium bis(salicylato)borate, trihexyltetradecylphosphonium bis(salicylato)borate, tributyltetradecylphosphonium bis(oxalato)borate, trihexyltetradecylphosphonium bis(oxalato)borate, tributyltetradecylphosphonium bis(malonato)borate, trihexyltetradecylphosphonium bis(malonato)borate, tributyltetradecylphosphonium bis(succinato)borate, trihexyltetradecylphosphonium bis(succinato)borate, tributyltetradecylphosphonium bis(glutarato)borate, trihexyltetradecylphosphonium bis(glutarato)borate, tributyltetradecylphosphonium bis(adipato)borate, trihexyltetradecylphosphonium bis(adipato)borate, choline bis(salicylato)borate, N-ethyl-N-methylpyrrolidinium bis(salicylato)borate, N-ethyl-N-methylpyrrolidinium bis(mandelato)borate, 1-ethyl-2,3-dimethylimidazolium bis(mandelato)borate, 1-ethyl-2,3-dimethylimidazolium bis(salicylato)borate, 1-methylimidazole-trimethylamine-BH2 bis(mandelato)borate, 1,2-dimethylimidazole-trimethylamine-BH2bis(mandelato)borate, 1-methylimidazole-trimethylamine-BH2 bis(salicylato)borate, and 1,2-dimethylimidazole-trimethylamine-BH2bis(salicylato)borate.
In one embodiment the lubricant component comprises trihexyltetradecylphosphonium bis(mandelato)borate.
In one embodiment the lubricant component comprises trihexyltetradecylphosphonium bis(salicylato)borate
In one embodiment the lubricant component comprises trihexyltetradecylphosphonium bis(oxalato)borate.
In one embodiment the lubricant component comprises trihexyltetradecylphosphonium bis(malonato)borate.
In a second aspect there is provided a lubricant comprising 0.05-100 wt % of the lubricant component described herein. The lubricant component can both be used in pure form and as an additive to other lubricants. If the lubricant component is used in pure form the lubricant component itself is the sole lubricant.
In one embodiment the lubricant comprises 0.05-20 wt %, of the lubricant component as described herein. In one embodiment the lubricant comprises 0.1-5 wt %, of the lubricant component. In one embodiment the lubricant comprises 0.5-5 wt %, of the lubricant component.
In a third aspect there is provided use of the lubricant component as described herein for at least one selected from reducing wear and reducing friction.
In a fourth aspect there is provided a method for reducing friction comprising use of a lubricant with the lubricant component as described herein.
There is also provided a method for reducing wear comprising use of a lubricant with the lubricant component as described herein.
Advantages of the invention include that the replacement of BF4−, PF6− and halogen containing ions with more hydrophobic and halogen-free anions will avoid corrosion and toxicity.
Halogen-free boron based ionic liquids, (=hf−BILs) with these novel halogen-free boron-based anions make a lubricant hydrolytically stable. This will aid to avoid the formation of hydrofluoric acid (HF) in the lubricant in the course of exploitation of machines. HF is produced by the most commonly used anion (BF4−) and (PF6−) in ILs. The formation of HF from ionic liquids is one of the main limitations of such lubricants, because HF is highly corrosive towards metals. The present novel hf-BILs according to the invention do not have such limitations.
Based on tribological studies of ionic liquids with imidazolium, pyrrolidinium and cholinium (as cations) and halogen-based anions, we suggest that ionic liquids according to the invention, i.e. ionic liquids with tetraalkylphosphonium, imidazolium, pyrrolidinium and cholinium (as cations) and halogen-free orthoborate anions will have good tribological performance in addition to their advantage as being halogen-free. Some examples of these halogen-free orthoborate anions are bis(mandelato)borate, bis(salicylato)borate, bis(oxalato)borate, bis(malonato)borate, bis(succinato)borate, bis(glutarato)borate and bis(adipato)borate. An outstanding antiwear and friction-reducing effect for steel-aluminium contacts has been proven for orthoborate based tetraalkylphosphonium ionic liquids and the “key” role is orthoborate anions in ILs as lubricants regarding these technical effects.
The invention will be described more in detail below with reference to the accompanying drawings, in which:
Regarding n in R, R′=CnH2n+1 of tetraalkylphosphonium cations, it is noted that borate with shorter (both linear and branched) alkyl chains are less miscible in oils (in particular, with mineral oils), while longer chain alkyl groups (both linear and branched) have higher miscibility with mineral oils. Therefore, an increase in the length of alkyl groups (n) is expected to result in a more homogeneous lubricant. However, the length of R and R′ should be optimized for each specific type of the oil and an optimum temperature interval for the lubricant, because too long alkyl chains will lead to a lower mobility of the additive in lubricant and, therefore, to compromised both anti-wear and friction reducing efficiency of the additive. Therefore, n is at least 1 and could be up to about 80 without negatively affecting the performance of the compound according to the invention.
In order to be well miscible with today's engine oils, such as POA 40 and POA 60 (Statoil) having carbon chain lengths of 40 and 60 carbon atoms, respectively, the value of n should be no less than 40 and 60, respectively. Thus, in one embodiment n≦60. The limit n≦80 is motivated by possible future products of motor oils with even longer alkyl chains, supposedly up to at least n=80.
A skilled person can in the light of the description make a routine optimization experiment and determine a suitable value of n and branched or/and non-branched character of the alkyl groups in tetraalkylphosphonium, immidazolium and pyrrolidinium cations.
It is conceived to use the lubricant components for reducing friction and reducing wear on a number of different materials both metals and non-metals. Examples of non-metals include but are not limited to ceramics with/without DLC (diamond-like-coatings) or/and graphene-based coatings. Examples of metals include but are not limited to alloys, steel, and aluminium with/without DLC (diamond-like-coatings) or/and graphene-based coatings.
A new family of hf-BILs was synthesized and purified following an improved protocol and a detailed study of their tribological and physicochemical properties including thermal behavior, density and viscosity, was carried out. The tribological properties were studied with 100Cr6 steel balls on an AA2024 aluminum disc in a rotating pin-on-disc test.
All compounds tested from this novel class of hf-BILs have outstanding antiwear as well as friction performance as compared with the fully formulated engine oil.
Synthesis schemes for the halogen free boron based ionic liquids according to the invention are shown below:
All novel halogen-free boron based ionic liquids (hf-BILs) were synthesized and purified using a modified literature methods.
Mandelic acid (3.043 g, 20 mmol) was added slowly to an aqueous solution of lithium carbonate (0.369 g, 5 mmol) and boric acid (0.618 g, 10 mmol) in 50 mL water. The solution was heated up to about 60° C. for two hours. The reaction was cooled to room temperature and tributyloctylphosphonium chloride (3.509 g, 10 mmol) was added. The reaction mixture was stirred for two hours at room temperature. The organic layer of reaction product formed was extracted with 80 mL of CH2Cl2. The CH2Cl2 organic layer was washed three times with 60 mL water. The CH2Cl2 was rotary evaporated at reduced pressure and product was dried in a vacuum oven at 60 for 2 days. A viscous colorless ionic liquid was obtained in 84% yield (5.30 g). m/z ESI-MS (−): 311.0 [BMB]−; m/z ESI-MS (+): 315.3 [P4448]+.
The procedure is similar to that used in the synthesis of [P4448][BMB]. The reaction started with (0.369 g, 5 mmol) of lithium carbonate, (0.618 g, 10 mmol) of boric acid, (3.043 g, 20 mmol) of mandelic acid and tributyltetradecylphosphonium chloride (4.349 g, 10 mmol). A viscous colorless ionic liquid was obtained in 81% yield (5.75 g). m/z ESI-MS (−): 310.9 [BMB]−; m/z ESI-MS (+): 399.2 [P44414]+.
The procedure is similar to that used in the synthesis of [P4448][BMB]. The reaction started with (0.369 g, 5 mmol) of lithium carbonate, (0.618 g, 10 mmol) of boric acid, (3.043 g, 20 mmol) of mandelic acid and trihexyltetradecylphosphonium chloride (5.189 g, 10 mmol). A viscous colorless ionic liquid was obtained in 91% yield (7.25 g). m/z ESI-MS (−): 311.0 [BMB]−; m/z ESI-MS (+): 483.3 [P66614]+.
The procedure is similar to that used in the synthesis of [P4448][BMB]. The reaction started with (0.369 g, 5 mmol) of lithium carbonate, (0.618 g, 10 mmol) of boric acid, (2.762 g, 20 mmol) of salicylic acid and tributyloctylphosphonium chloride (3.509 g, 10 mmol). A viscous colorless ionic liquid was obtained in 88% yield (5.28 g). m/z ESI-MS (−): 283.1 [BScB]−; m/z ESI-MS (+): 315.3 [P4448]+.
The procedure is similar to that used in the synthesis of [P4448][BMB]. The reaction started with (0.369 g, 5 mmol) of lithium carbonate, (0.618 g, 10 mmol) of boric acid, (2.762 g, 20 mmol) of salicylic acid and tributyltetradecylphosphonium chloride (4.349 g, 10 mmol). A viscous colorless ionic liquid was obtained in 94% yield (6.44 g). m/z ESI-MS (−): 283.0 [BScB]−; m/z ESI-MS (+): 399.4 [P44414]+.
The procedure is similar to that used in the synthesis of [P4448][BMB]. The reaction started with (0.369 g, 5 mmol) of lithium carbonate, (0.618 g, 10 mmol) of boric acid, (2.762 g, 20 mmol) of salicylic acid and trihexyltetradecylphosphonium chloride (5.189 g, 10 mmol). A viscous colorless ionic liquid was obtained in 95% yield (7.30 g). m/z ESI-MS (−): 283.0 [BScB]−; m/z ESI-MS (+): 483.5 [P66614]+.
The procedure is similar to that used in the synthesis of [P4448][BMB]. The reaction started with (0.369 g, 5 mmol) of lithium carbonate, (0.618 g, 10 mmol) of boric acid, (1.80 g, 20 mmol) of oxalic acid and tributyltetradecylphosphonium chloride (4.349 g, 10 mmol). A viscous colorless ionic liquid was obtained.
The procedure is similar to that used in the synthesis of [P4448][BMB]. The reaction started with (0.369 g, 5 mmol) of lithium carbonate, (0.618 g, 10 mmol) of boric acid, (1.80 g, 20 mmol) of oxalic acid and trihexyltetradecylphosphonium chloride (5.189 g, 10 mmol). A viscous colorless ionic liquid was obtained. m/z ESI-MS (−): [BOB]−; m/z ESI-MS (+): 483.5 [P66614]+.
The procedure is similar to that used in the synthesis of [P4448][BMB]. The reaction started with (0.369 g, 5 mmol) of lithium carbonate, (0.618 g, 10 mmol) of boric acid, (2.081 g, 20 mmol) of malonic acid and tributyltetradecylphosphonium chloride (4.349 g, 10 mmol). A viscous colorless ionic liquid was obtained.
The procedure is similar to that used in the synthesis of [P4448][BMB]. The reaction started with (0.369 g, 5 mmol) of lithium carbonate, (0.618 g, 10 mmol) of boric acid, (2.081 g, 20 mmol) of malonic acid and trihexyltetradecylphosphonium chloride (5.189 g, 10 mmol). A viscous colorless ionic liquid was obtained. m/z ESI-MS (−): [BMLB]−; m/z ESI-MS (+): 483.5 [P66614]+.
The procedure is similar to that used in the synthesis of [P4448][BMB]. The reaction started with (0.369 g, 5 mmol) of lithium carbonate, (0.618 g, 10 mmol) of boric acid, (2.362 g, 20 mmol) of succinic acid and tributyltetradecylphosphonium chloride (4.349 g, 10 mmol). A viscous colorless ionic liquid was obtained.
The procedure is similar to that used in the synthesis of [P4448][BMB]. The reaction started with (0.369 g, 5 mmol) of lithium carbonate, (0.618 g, 10 mmol) of boric acid, (2.362 g, 20 mmol) of succinic acid and trihexyltetradecylphosphonium chloride (5.189 g, 10 mmol). A viscous colorless ionic liquid was obtained.
The procedure is similar to that used in the synthesis of [P4448][BMB]. The reaction started with (0.369 g, 5 mmol) of lithium carbonate, (0.618 g, 10 mmol) of boric acid, (2.642 g, 20 mmol) of glutaric acid and tributyltetradecylphosphonium chloride (4.349 g, 10 mmol). A viscous colorless ionic liquid was obtained.
The procedure is similar to that used in the synthesis of [P4448][BMB]. The reaction started with (0.369 g, 5 mmol) of lithium carbonate, (0.618 g, 10 mmol) of boric acid, (2.642 g, 20 mmol) of glutaric acid and trihexyltetradecylphosphonium chloride (5.189 g, 10 mmol). A viscous colorless ionic liquid was obtained.
The procedure is similar to that used in the synthesis of [P4448][BMB]. The reaction started with (0.369 g, 5 mmol) of lithium carbonate, (0.618 g, 10 mmol) of boric acid, (2.923 g, 20 mmol) of adipic acid and tributyltetradecylphosphonium chloride (4.349 g, 10 mmol). A viscous colorless ionic liquid was obtained.
The procedure is similar to that used in the synthesis of [P4448][BMB]. The reaction started with (0.369 g, 5 mmol) of lithium carbonate, (0.618 g, 10 mmol) of boric acid, (2.923 g, 20 mmol) of adipic acid and trihexyltetradecylphosphonium chloride (5.189 g, 10 mmol). A viscous colorless ionic liquid was obtained.
Salicylic acid (5.524 g, 40 mmol) was added slowly to an aqueous solution of lithium carbonate (0.738 g, 10 mmol) and boric acid (1.236 g, 20 mmol) in 40 mL water. The solution was heated upto about 60° C. for two hours. The reaction was cooled to room temperature and choline chloride (2.792 g, 20 mmol) was added. The reaction mixture was stirred for two hours at room temperature. The organic layer of reaction product formed was extracted with 80 mL of CH2Cl2. The CH2Cl2 organic layer was washed three times with 80 mL water. The CH2Cl2 was rotary evaporated at reduced pressure and the product was dried in a vacuum oven at 60 for 2 days. A white solid ionic liquid was recrystallized from CH2Cl2 (5.44 g, 70% yield). m/z ESI-MS (−): 283.0 [BScB]−; m/z ESI-MS (+): 103.9 [Choline]+.
Salicylic acid (5.524 g, 40 mmol) was added slowly to an aqueous solution of lithium carbonate (0.738 g, 10 mmol) and boric acid (1.236 g, 20 mmol) in 40 mL water. The solution was heated upto about 60° C. for two hours. The reaction was cooled to room temperature and N-ethyl-N-methylpyrrolidinium iodide (4.822 g, 20 mmol) was added. The reaction mixture was stirred for two hours at room temperature. The organic layer of reaction product formed was extracted with 80 ml of CH2Cl2. The CH2Cl2 organic layer was washed three times with 80 mL water. The CH2Cl2 was rotary evaporated at reduced pressure and the product was dried in a vacuum oven at 60 for 2 days. A white solid ionic liquid was recrystallized from CH2Cl2 (6.167 g, 78% yield). m/z ESI-MS (−): 283.0 [BScB]−; m/z ESI-MS (+): 113.9 [EMPy]+.
The procedure is similar to that used in the synthesis of [EMPy][BScB]. The reaction started with lithium carbonate (0.369 g, 5 mmol), boric acid (0.618 g, 10 mmol), mandelic acid (3.043 g, 20 mmol) and N-ethyl-N-methylpyrrolidinium iodide (2.41 g, 10 mmol). A viscous ionic liquid was obtained in 67% yield (2.85 g). MS (ESI) calcd for [C6H16N]+ m/z 114.2. found m/z 114.1; calcd for [C16H12O6B]− m/z 311.0. found m/z 311.0.
Mandelic acid (3.043 g, 20 mmol) was added slowly to an aqueous solution of lithium carbonate (0.369 g, 5 mmol) and boric acid (0.618 g, 10 mmol) in 50 mL water. The solution was heated upto about 60° C. for two hours. The reaction was cooled to room temperature and 1-ethyl-2,3-dimethylimidazolium iodide (2.52 g, 10 mmol) was added. The reaction mixture was stirred for two hours at room temperature. The bottom layer of the reaction product formed was extracted with 80 mL of CH2Cl2. The CH2Cl2 organic layer was washed three times with 100 mL water. The CH2Cl2 was rotary evaporated at reduced pressure and the final product was dried in a vacuum oven at 60° C. for 2 days. A viscous ionic liquid was obtained in 78% yield (3.40 g).
MS (ESI) calcd for [C7H13N2]+ m/z 125.2. found m/z 125.2; calcd for [C16H12O6B]− m/z 311.0. found m/z 311.1.
The procedure is similar to that used in the synthesis of [EMIm][BMB]. The reaction started with lithium carbonate (0.369 g, 5 mmol), boric acid (0.618 g, 10 mmol), salicylic acid (2.762 g, 20 mmol) and 1-ethyl-2,3-dimethylimidazolium iodide (2.52 g, 10 mmol). A white solid product was obtained in 83% yield (3.38 g). MS (ESI) calcd for [C7H13N2]+ m/z 125.2. found m/z 125.1; calcd for [C14H8O6B]− m/z 283.0. found m/z 283.0.
Mandelic acid (3.043 g, 20 mmol) was added slowly to an aqueous solution of lithium carbonate (0.369 g, 5 mmol) and boric acid (0.618 g, 10 mmol) in 50 mL water. The solution was heated upto about 60° C. for two hours. The reaction was cooled to room temperature and 1-methylimidazole trimethylamine BH2 iodide (2.70 g, 10 mmol) was added. The reaction mixture was stirred for two hours at room temperature. The bottom layer of the reaction product formed was extracted with 80 mL of CH2Cl2. The CH2Cl2 organic layer was washed three times with 100 mL water. The CH2Cl2 was rotary evaporated at reduced pressure and the final product was dried in a vacuum oven at 60° C. for 2 days.
The procedure is similar to that used in the synthesis of [MimN111BH2][BMB]. The reaction started with lithium carbonate (0.369 g, 5 mmol), boric acid (0.618 g, 10 mmol), mandelic acid (3.043 g, 20 mmol) and 1,2-dimethylimidazole trimethylamine BH2 iodide (2.841 g, 10 mmol) was added. A liquid product was obtained.
Salicylic acid (5.524 g, 40 mmol) was added slowly to an aqueous solution of lithium carbonate (0.738 g, 10 mmol) and boric acid (1.236 g, 20 mmol) in 40 mL water. The solution was heated upto about 60° C. for two hours. The reaction was cooled to room temperature and 1-methylimidazole trimethylamine BH2 iodide (5.40 g, 20 mmol) was added. The reaction mixture was stirred for two hours at room temperature. The organic layer of reaction product formed was extracted with 80 ml of CH2Cl2. The CH2Cl2 organic layer was washed three times with 80 mL water. The CH2Cl2 was rotary evaporated at reduced pressure and the product was dried in a vacuum oven at 60 for 2 days. A liquid product was obtained.
The procedure is similar to that used in the synthesis of [MImN111BH2][BScB]. The reaction started with lithium carbonate (0.369 g, 5 mmol), boric acid (0.618 g, 10 mmol), salicylic acid (2.762 g, 20 mmol) and 1,2-dimethylimidazole trimethylamine BH2 iodide (2.841 g, 10 mmol) was added. A liquid product was obtained.
NMR experiments were collected on a Bruker Avance 400 (9.4 Tesla magnet) with a 5 mm broadband autotunable probe with Z-gradients at 30° C. NMR spectra were collected and processed using the spectrometer “Topspin” 2.1 software. 1H and 13C spectra were reference to internal TMS and CDCl3. External references were employed in the 31P (85% H3PO4) and 11B (Et2O.BF3).
The positive and negative ion electrospray mass spectra were obtained with a Micromass Platform 2 ESI-MS instrument.
A Q100 TA instrument was used for differential scanning calorimetric (DSC) measurements to study the thermal behavior of hf-BILs. An average weight of 5-10 mg of each sample was sealed in an aluminum pan and cooled to −120° C. then heated upto 50° C. at a scanning rate of 10.0° C./min.
Viscosity of these hf-BILs was measured with an AMVn Automated Microviscometer in a temperature range from 20 to 90° C. using a sealed sample tube.
The wear tests were conducted at room temperature (22° C.) on a Nanovea pin-on-disk tester according to ASTM G99 using 6 mm 100Cr6 balls on 45 mm diameter AA2024 aluminum disks. The composition, Vicker's hardness and average roughness, Ra, of the steel balls and aluminum disks are shown in Table 1. The disks were lubricated with 0.1 mL of lubricant. Experiments were conducted at loads of 20 and 40 N for a distance of 1000 m, with a wear track diameter of 20 mm and a speed of 0.2 m/s. The friction coefficient was recorded throughout the experiment. On completion of the wear tests, the wear depth was measured using a Dektak 150 stylus profilometer.
Thermal Behaviour of hf-BILs
For common orthoborate anions with different phosphonium cations, a decrease in Tg is observed with an increase in size of alkyl chains in the cations. This trend is more easily seen in hf-BILs with the BScW anion and different phosphonium cations: Tg fall in the order P4448+ (−49° C.)>P44414+ (−54° C.)>P66616+ (−56° C.) (see Table 2). Del Sesto et al. have observed a similar trend for ionic liquids of phosphonium cations with bistrifylamide (NTf2) and dithiomaleonitrile (dtmn) anions. Lowest Tg of hf-BILs (down to −73° C. for P66614-BMLB) are reached with P66616+ as the cation, probably because of a larger size, lower symmetry and a low packing efficiency of this cation.
Density Measurements of hf-BILs
Dynamic viscosity of hf-BILs
Some of novel hf-BILs have shown very high viscosity in the temperature range between 20-30° C., which was not measurable by the viscometer used in this study. However, viscosity of hf-BILs decreases markedly with an increase in temperature (from ca 1000 cP at ca 20° C. down to ca 20 cP at ca 90° C., see
Tribological Performance of hf-BILs
Mean friction coefficients for the selected hf-BILs in comparison with 15W-50 engine oil are shown in
At the load of 40 N the friction coefficient for the 15W-50 engine oil varied considerably over a sliding distance. At the beginning of the test, the friction coefficient was stable but a sudden increase occurred at a sliding distance of ca 200 m and remained that high for a 400 m sliding distance. In the beginning of the test a thin tribofilm separated the surfaces and prevented them from a direct metal-to-metal contact. A sudden increase in the friction coefficient is the evidence of that the tribofilm formed by standard additives present in 15W-50 engine oil is not stable on aluminum surfaces.
To the contrary, novel hf-BILs according to the invention exhibit a different trend compared to than in the 15W-50 engine oil. In the case of P66614-BMB and P66614-BMLB, there was no increase in the friction coefficient over the whole period of the tribological test. The friction coefficients increased (for P66614-BScB and P66614-BOB) in the very beginning of the test, but then they stabilized after a sliding distance of 50 m. Thus, stable tribofilms (at least until 1000 m sliding distances) are formed at aluminum surfaces lubricated with novel hf-BILs already after a short sliding distance.
The tetraalkylphosphonium-orthoborate according to the invention based on phosphonium cations containing only P—C bonds are considerably more stable to hydrolysis compared for instance to compounds comprising P—N bonds. We have proven experimentally the hydrolytic stability of our novel hf-BILs. A small droplet of [P6,6,6,14] [BScB] was put in distilled water and left inside water for 10 days to confirm the hydrolytic stability of these hf-BILs. There was no change in appearance. The sample was analysed by ESI-MS; peaks at m/z 483.5 and m/z 283.0 for [C32H68P]+ and [C14H8O6B]−, respectively, and the absence of other peaks in ESI-MS spectra confirmed the hydrolytic stability of these hf-BILs.
| Number | Date | Country | Kind |
|---|---|---|---|
| 1150255-6 | Mar 2011 | SE | national |
This application is a 371 U.S. National Stage of International Application No. PCT/SE2012/050317, filed Mar. 22, 2012, and claims priority to Swedish Patent Application No. 1150255-6, filed Mar. 22, 2011, the disclosures of which are herein incorporated by reference in their entirety.
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/SE12/50317 | 3/22/2012 | WO | 00 | 9/19/2013 |
