JP6826350B2 - Synthetic lubricating oil - Google Patents

Description

The present invention relates to synthetic lubricating oils and lubricating oil compositions that are useful as main components of various lubricating oils and lubricating oil compositions. In particular, the present invention relates to a synthetic lubricating oil having a relatively good lubricity at a high temperature from room temperature to about 100 ° C. and a viscosity index of 200 or more, and a lubricating oil composition containing the synthetic lubricating oil.

In recent years, devices and machines used in various industrial fields such as automobiles, home appliances, electronic devices, and industrial machines are required to improve the performance of lubricating oil and to have appropriately adjusted lubricating performance. That is, not only improvement of conventional equipment such as speeding up and miniaturization of equipment and machines, but also lubrication performance that can withstand more severe usage conditions according to each equipment and machine newly developed in various fields. Not only that, there is an increasing need for lubrication performance that is properly adjusted by equipment and machines.

Lubricating oils usually consist of a base oil and an additive depending on the application. The base oil is a base material that controls the basic characteristics of the lubricating oil, and is a mineral oil, a synthetic oil, or the like.
Mineral oil is a refined lubricating oil fraction of petroleum, is generally inexpensive, and has been widely used from the past to the present (see Non-Patent Document 1). However, mineral oil is inferior in heat resistance, is easily oxidized and deteriorated, and is inferior in durability. Furthermore, due to variations in the molecular structure, it has become difficult to obtain lubrication performance that is highly suitable for each device or machine. In order to improve heat resistance and durability, various additives are sometimes blended, but there are cases where the blending of additives is restricted depending on the type and application of the device or machine.

On the other hand, synthetic oil is produced through an advanced and complicated process, impurities are eliminated as much as possible, and it is said that relatively high heat resistance and less variation in lubrication performance can be obtained. Although synthetic oils are more expensive than mineral oils, hydrocarbon-based, ester-based, ether-based, silicon-based, and fluorine-based oils have been developed and used to date, depending on the application and usage mode. (See Non-Patent Document 1).
Further, Patent Document 1 describes a method for preparing a branched siloxane such as methyltris (trimethylsiloxy) silane, which is useful as an industrial siloxane lubricant, a cosmetic fluid, a cleaning agent, and the like.
Further, Non-Patent Documents 3 and 4 describe a method for preparing tetrakis (trimethylsilyloxy) silane and phenyltris (trimethylsilyloxy) silane and their viscosities.

U.S. Patent 2002/0133035A1

http://www.juntsu.co.jp/qa/qa0111.html J.Am.Chem.Soc., 1999,121 (15), pp.3693-3703. J.Am.Chem.Soc., 1949,71 (9), pp.3235-3254. Silicon Compounds: Silanes and Silicones, Gelest, Inc., 2008, p.344.

As described above, the synthetic oil has relatively high heat resistance and can obtain lubrication performance with little variation. However, for example, PAO (poly-α-olefin) synthetic oils used in automobiles and the like have a viscosity index of only about 120 to 140. Further, neither Patent Document 1 nor Non-Patent Documents 3 and 4 describe at all about using a synthetic oil having a high viscosity index. As described above, a synthetic oil having a kinematic viscosity at 100 ° C. of 2.0 or more mm ² / sec and a viscosity index of 200 or more, which can be used for high-temperature lubrication applications, is not known.

The present invention has been made against the background of the above-mentioned prior art and its problems, and is a synthesis in which the kinematic viscosity at 100 ° C. is 2.0 to 7.0 mm ² / sec and the viscosity index is 200 or more. The subject is to provide lubricating oil.

As a result of diligent research to solve the above problems in various tests and research processes, the present inventor has a kinematic viscosity of a compound represented by the following formula (I) or a synthetic oil composed of a mixture of compounds at 100 ° C. 2 It was found that it exhibits lubrication performance of about .0 to 7.0 mm ² / sec and viscosity index of 200 or more.

The present invention has been completed based on the above-mentioned findings under the above-mentioned problems, and the following invention is provided in this case.
<1> Ri Do from a compound or mixture of compounds represented by the following formula (I), a kinematic viscosity of 100 ° C. is 2.0~7.0mm ² / sec, der Ru synthetic lubricating viscosity index of 200 or more oil.
R ⁰ _n Si (OSiMe ₂ R ¹ ) _4-n (I)
(In the formula, R ⁰ is a phenyl group which may have an alkyl group having 1 to 3 carbon atoms and a substituent of a halogen atom , and Me is a methyl group. (4-n) R ^1s are , An aryl group, a linear or branched hydrocarbon group having 6 to 15 carbon atoms which may have a substituent of a halogen atom, and may be the same as or different from each other. 0 or 1)
< 2 > A lubricating oil composition containing the synthetic lubricating oil according to <1>.
< 3 > A lubricating oil composition using the synthetic lubricating oil according to <1> as a base oil.

The present invention can include the following aspects.
<5> A synthetic lubricating oil composed of a compound represented by the following formula (II) or a mixture of compounds.
Si (OSiMe ₂ R ¹ ) ₄ (II)
(Wherein, Me is a methyl group. Compound 4 R ¹ in each molecule is a linear or branched alkyl group having from 6 to 15 carbon atoms, may be the same as each other, or different May be.)
<6> A synthetic lubricating oil composed of a compound represented by the following formula (III) or a mixture of compounds.
R ⁰ ₁ Si (OSiMe ₂ R ¹ ) ₃ (III)
(In the formula, R ⁰ is an phenyl group, Me represents R ¹ in three in a methyl group. Compounds each molecule is a linear or branched alkyl group having from 6 to 15 carbon atoms, identical to one another It may or may not be different.)
<7> A lubricating oil composition containing the synthetic lubricating oil according to <5> or <6>.
In addition, in this specification, "~" indicating a numerical range is used as a meaning including numerical values described before and after the numerical range as a lower limit value and an upper limit value.

The synthetic lubricating oil of the present invention has a kinematic viscosity of 2.0 to 7.0 mm ² / sec at 100 ° C. and a viscosity index of 200 or more, and is in a high temperature environment from normal temperature to at least slightly higher than 100 ° C. Can be suitably used in.

The synthetic lubricating oil of the present invention comprises a compound represented by the general formula (I) or a mixture of compounds, has a kinematic viscosity at 100 ° C. of 2.0 to 7.0 mm ² / sec, and has a viscosity index. Shows more than 200 lubrication performance.
R ⁰ _n Si (OSiMe ₂ R ¹ ) _4-n (I)
(In the formula, R ⁰ is an phenyl group, Me is a methyl group. (4-n) pieces of R ¹ is a linear or branched hydrocarbon group having from 6 to 15 carbon atoms, identical to each other It may be different, or n may be 0 or 1.)

The above R ⁰ is a phenyl group and may have a substituent such as an alkyl group having 1 to 3 carbon atoms or a halogen atom.
R ¹ is a linear or branched hydrocarbon group having 6 to 15 carbon atoms, and may have a substituent such as an aryl group or a halogen atom. It is preferably a linear or branched alkyl group having 6 to 15 carbon atoms, and more preferably a linear alkyl group having 6 to 10 carbon atoms. Specific examples thereof include a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tridecylic group, a tetradecyl group and the like.

The synthetic lubricating oil of the present invention may be produced by any method, and for example, according to the synthetic method disclosed in Non-Patent Document 2, Tetrakis as the following formula (1) or (2). It can be produced by reacting (dimethylsilyloxy) silane or phenyltris (dimethylsilyloxy) silane with 1-alkene.

(式中、Ａ¹は、炭素数４〜１３の直鎖状又は分岐状炭化水素基であり、Ｒ¹は、炭素数６〜１５の直鎖状又は分岐状炭化水素基である。)

(In the formula, A ¹ is a linear or branched hydrocarbon group having 4 to 13 carbon atoms, and R ¹ is a linear or branched hydrocarbon group having 6 to 15 carbon atoms.)

(式中、Ａ¹は、炭素数４〜１３の直鎖状又は分岐状炭化水素基であり、Ｒ¹は、炭素数６〜１５の直鎖状又は分岐状炭化水素基である。)

(In the formula, A ¹ is a linear or branched hydrocarbon group having 4 to 13 carbon atoms, and R ¹ is a linear or branched hydrocarbon group having 6 to 15 carbon atoms.)

In addition to the above, the synthetic lubricating oil of the present invention reacts two types of 1-alkene with tetrakis (dimethylsilyloxy) silane or phenyltris (dimethylsilyloxy) silane as described in the following formula (3) or (4). By doing so, it can also be produced as a mixture containing compounds having different hydrocarbon groups in the molecular structure of the synthetic lubricating oil.

(式中、Ａ¹≠Ａ²であって、Ａ¹及びＡ²は、炭素数４〜１３の直鎖状又は分岐状炭化水素基である。Ｒ¹≠Ｒ²であって、Ｒ¹及びＲ²は、炭素数６〜１５の直鎖状又は分岐状炭化水素基である。)

(In the equation, A ¹ ≠ A ² and A ¹ and A ² are linear or branched hydrocarbon groups having 4 to 13 carbon atoms. R ¹ ≠ R ² and R ¹ and R ² is a linear or branched hydrocarbon group having 6 to 15 carbon atoms.)

(式中、Ａ¹≠Ａ²であって、Ａ¹及びＡ²は、炭素数４〜１３の直鎖状又は分岐状炭化水素基である。Ｒ¹≠Ｒ²であって、Ｒ¹及びＲ²は、炭素数６〜１５の直鎖状又は分岐状炭化水素基である。)

(In the equation, A ¹ ≠ A ² and A ¹ and A ² are linear or branched hydrocarbon groups having 4 to 13 carbon atoms. R ¹ ≠ R ² and R ¹ and R ² is a linear or branched hydrocarbon group having 6 to 15 carbon atoms.)

The synthetic lubricating oil of the present invention may be used as it is as a lubricating oil, or may be used as a base oil (50 wt% or more of the composition) of the lubricating oil composition. It can also be used as an additive component (for example, 1 to 40 wt% of the lubricating oil composition) for the purpose of improving the high temperature lubrication characteristics of mineral oil and other synthetic oils.

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples.

[Example 1]
<Synthesis of Tetrakis (Hexyldimethylsilyloxy) Silane (Compound 1a: R ¹ = Hexil) (Formula 1)>
1-Hexene (11) in a toluene (80 mL) solution containing tetrakis (dimethylsilyloxy) silane (9.25 g, 28.1 mmol) and a Karstedt catalyst (94 mg, 19.0-21.5% as Pt) under a nitrogen atmosphere. A solution of .1 g, 132 mmol) of toluene (50 mL) was added, and the mixture was stirred at room temperature for 6 hours. After concentrating the reaction mixture under reduced pressure, the residue was purified by silica gel column chromatography (elution: hexane) to obtain 16.3 g (yield 80%) of compound 1a (colorless liquid).
^{1 1} H NMR (CDCl ₃ , 500 MHz): δ = 0.06 (s, 24H), 0.50-0.56 (m, 8H), 0.88 (t, J = 7.0Hz, 12H), 1 .22-1.37 (m, 32H).
¹³ C NMR (CDCl ₃ , 125 MHz): δ = -0.07, 14.14, 18.19, 22.65, 23.12, 31.69, 33.27.

[Example 2]
<Synthesis of tetrakis (decyldimethylsilyloxy) silane (Compound 1b: R ¹ = decyl) (Formula 1)>
1-decene (14) in a toluene (80 mL) solution containing tetrakis (dimethylsilyloxy) silane (7.42 g, 22.6 mmol) and a Karstedt catalyst (72 mg, 19.0-21.5% as Pt) under a nitrogen atmosphere. A solution of .6 g, 104 mmol) in toluene (50 mL) was added, and the mixture was stirred at room temperature for 6 hours. After concentrating the reaction mixture under reduced pressure, the residue was purified by silica gel column chromatography (elution: hexane) to obtain 16.8 g (yield 84%) of compound 1b (colorless liquid).
^{1 1} H NMR (CDCl ₃ , 500 MHz): δ = 0.06 (s, 24H), 0.50-0.56 (m, 8H), 0.88 (t, J = 7.0Hz, 12H), 1 .21-1.37 (m, 64H).
¹³ C NMR (CDCl ₃ , 125 MHz): δ = -0.06, 14.12, 18.20, 22.71, 23.19, 29.40, 29.51, 29.71, 29.75, 31 .96, 33.65.

[Example 3]
<Synthesis of Tetrakis (Tridecyldimethylsilyloxy) Silane (Compound 1c: R ¹ = Tridecylic) (Formula 1)>
1-Tridecene (19) in a toluene (80 mL) solution containing tetrakis (dimethylsilyloxy) silane (7.47 g, 22.7 mmol) and a Karstedt catalyst (72 mg, 19.0-21.5% as Pt) under a nitrogen atmosphere. A solution of .2 g, 105 mmol) in toluene (50 mL) was added and stirred at room temperature for 6 hours. After concentrating the reaction mixture under reduced pressure, the residue was purified by silica gel column chromatography (elution: hexane) to obtain 17.3 g (yield 72%) of compound 1c (colorless liquid).
^{1 1} H NMR (CDCl ₃ , 500 MHz): δ = 0.06 (s, 24H), 0.50-0.56 (m, 8H), 0.88 (t, J = 7.0Hz, 12H), 1 .19-1.37 (m, 88H).
¹³ C NMR (CDCl ₃ , 125 MHz): δ = -0.05, 14.12, 18.20, 22.71, 23.19, 29.40, 29.52, 29.71 (2C), 29. 75 (2C), 29.81, 31.95, 33.65.

[Example 4]
<Synthesis of Phenyltris (Hexyldimethylsilyloxy) Silane (Compound 2a: R ¹ = Hexil) (Formula 2)>
1-Hexene (80 mL) in a toluene (80 mL) solution containing phenyltris (dimethylsilyloxy) silane (11.6 g, 35.2 mmol) and a Karstedt catalyst (48 mg, 19.0 to 21.5% as Pt) under a nitrogen atmosphere. A solution of 11.0 g (131 mmol) in toluene (50 mL) was added, and the mixture was stirred at room temperature for 4 hours. The reaction mixture was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (elution: hexane) to obtain 19.5 g (yield 95%) of compound 2a (colorless liquid).
^{1 1} H NMR (CDCl ₃ , 500 MHz): δ = 0.08 (s, 18H), 0.50-0.58 (m, 6H), 0.87 (t, J = 7.0Hz, 9H), 1 .18-1.36 (m, 24H), 7.26-7.39 (m, 3H), 7.52-7.56 (m, 2H).
¹³ C NMR (CDCl ₃ , 125 MHz): δ = 0.15, 14.13, 18.28, 22.661.231.14, 31.64, 33.19, 127.42, 129.37, 133. 84, 135.68.

[Example 5]
<Synthesis of Phenyltris (decyldimethylsilyloxy) silane (Compound 2b: R ¹ = Decyl) (Formula 2)>
1-decene (80 mL) in a toluene (80 mL) solution containing phenyltris (dimethylsilyloxy) silane (12.6 g, 38.2 mmol) and a Karstedt catalyst (67 mg, 19.0-21.5% as Pt) under a nitrogen atmosphere. A solution of 18.6 g (133 mmol) in toluene (50 mL) was added, and the mixture was stirred at room temperature for 4 hours. After concentrating the reaction mixture under reduced pressure, the residue was purified by silica gel column chromatography (elution: hexane) to obtain 25.7 g (yield 89%) of compound 2b (colorless liquid).
^{1 1} H NMR (CDCl ₃ , 500 MHz): δ = 0.08 (s, 18H), 0.51-0.58 (m, 6H), 0.88 (t, J = 7.0Hz, 9H), 1 .18-1.36 (m, 48H), 7.29-7.39 (m, 3H), 7.52-7.56 (m, 2H).
¹³ C NMR (CDCl ₃ , 125 MHz): δ = 0.16, 14.12, 18.28, 22.71, 23.20, 29.38, 29.44, 29.66, 29.72, 31. 95, 33.56, 127.42, 129.36, 133.84, 135.68.

[Example 6]
<Synthesis of Phenyltris (Undecylic Dimethylsilyloxy) Silane (Compound 2c: R ¹ = Undecylic) (Formula 2)>
1-Undecene (80 mL) in a toluene (80 mL) solution containing phenyltris (dimethylsilyloxy) silane (11.8 g, 35.6 mmol) and Karstedt catalyst (78 mg, 19.0-21.5% as Pt) under a nitrogen atmosphere A solution of 19.1 g (124 mmol) in toluene (50 mL) was added, and the mixture was stirred at room temperature for 4 hours. The reaction mixture was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (elution: hexane) to obtain 25.6 g (yield 91%) of compound 2c (colorless liquid).
^{1 1} H NMR (CDCl ₃ , 500 MHz): δ = 0.08 (s, 18H), 0.51-0.58 (m, 6H), 0.88 (t, J = 7.0Hz, 9H), 1 .18-1.36 (m, 54H), 7.29-7.39 (m, 3H), 7.52-7.56 (m, 2H).
¹³ C NMR (CDCl ₃ , 125 MHz): δ = 0.16, 14.13, 18.29, 22.71, 23.20, 29.40, 29.45, 29.66, 29.69, 29. 78, 31.96, 33.57, 127.42, 129.36, 133.84, 135.68.

[Example 7]
<Synthesis of Phenyltris (Pentadecyldimethylsilyloxy) Silane (Compound 2d: R ¹ = Pentadecylic) (Formula 2)>
1-Pentadecene (80 mL) in a toluene (80 mL) solution containing phenyltris (dimethylsilyloxy) silane (9.09 g, 27.5 mmol) and a Karstedt catalyst (68 mg, 19.0-21.5% as Pt) under a nitrogen atmosphere. A solution of 19.6 g, 93.3 mmol) in toluene (50 mL) was added, and the mixture was stirred at room temperature for 4 hours. After concentrating the reaction mixture under reduced pressure, the residue was purified by silica gel column chromatography (elution: hexane) to obtain 20.9 g (yield 79%) of compound 2d (colorless liquid).
^{1 1} H NMR (CDCl ₃ , 500 MHz): δ = 0.08 (s, 18H), 0.51-0.58 (m, 6H), 0.88 (t, J = 7.0Hz, 9H), 1 .18-1.36 (m, 78H), 7.29-7.39 (m, 3H), 7.52-7.56 (m, 2H).
¹³ C NMR (CDCl ₃ , 125 MHz): δ = 0.17, 14.13, 18.30, 22.72, 23.21, 29.41, 29.47, 29.68, 29.71, 29. 76 (4C), 29.79, 31.97, 33.58, 127.43, 129.37, 133.85, 135.69.

[Example 8]
<Synthesis of mixture A (R ¹ = hexyl, R ² = octyl) (Equation 3)>
1-Hexene (7) in a toluene (62 mL) solution containing tetrakis (dimethylsilyloxy) silane (10.4 g, 31.6 mmol) and a Karstedt catalyst (94 mg, 19.0 to 21.5% as Pt) under a nitrogen atmosphere. A .10 g, 64.3 mmol) toluene (15 mL) solution was added and stirred at room temperature for 2 hours, then a 1-octene (6.95 g, 82.6 mmol) toluene (15 mL) solution was added and stirred at room temperature for 2 hours. .. The reaction mixture was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (elution: hexane) to obtain 21.3 g of the mixture A (colorless liquid).

[Example 9]
<Synthesis of mixture B (R ¹ = hexyl, R ² = tridecylic acid) (Equation 4)>
1-Tridecene (62 mL) in a toluene (62 mL) solution containing phenyltris (dimethylsilyloxy) silane (13.3 g, 40.2 mmol) and a Karstedt catalyst (56 mg, 19.0 to 21.5% as Pt) under a nitrogen atmosphere. Add 14.7 g, 64.3 mmol) of toluene (20 mL) and stir at room temperature for 2 hours, then add 1-hexene (4.43 g, 52.6 mmol) of toluene (10 mL) and stir at room temperature for 2 hours. did. The reaction mixture was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (elution: hexane) to obtain 25.9 g of the mixture B (colorless liquid).

[Example 10]
<Compounds 1a to 1c, 2a to 2d, kinematic viscosity and viscosity index of mixtures A and B>
The kinematic viscosities of the compounds 1a to 1c and 2a to 2d produced in Examples 1 to 9 and the mixtures A and B were measured by the method of JIS K 2283. The viscosity index was calculated by the method of JIS K 2283. Table 1 shows the kinematic viscosities of compounds 1a to 1c, 2a to 2d, and mixtures A and B at 40 ° C. and 100 ° C., and the viscosity index.

[Comparison example]
<Kinematic viscosity of compounds 1d and 2e>
The kinematic viscosities of the tetrakis (trimethylsilyloxy) silane (1d) and the phenyltris (trimethylsilyloxy) silane (2e) shown in [Chemical Formula 5] are shown in Table 2 (Non-Patent Documents 3 and 4). The kinematic viscosity of compound 1d was calculated from the literature values with a density of 0.9. The viscosity is not measured at 100 ° C., the value of 60 ° C. for 1d is less than 2.0 mm ² / sec, a kinematic viscosity of 100 ° C. of 2e is expected to be less than 2.0 mm ² / sec. Therefore, it is not possible to calculate the viscosity index for these compounds. Since these compounds have a small kinematic viscosity of less than 2.0 mm ² / sec at 100 ° C., they cannot be used at high temperatures such as 100 ° C.

Since the synthetic lubricating oil of the present invention has an alkyl chain having a hexyl group or more, it exceeds 2.0 mm ² / sec even at 100 ° C. Therefore, it can be suitably used even in a high temperature environment from normal temperature to at least slightly higher than 100 ° C. Further, the viscosity index (viscosity index of 200 or more, preferably 220 or more) of the synthetic lubricating oil of the present invention is significantly larger than that of the currently used refined mineral oils and synthetic oils PAO (viscosity index 120 to 140). Therefore, it is considered that it can contribute to further improvement in performance and life of the equipment and further energy saving in the operation of the equipment.

Since the synthetic lubricating oil of the present invention has a kinematic viscosity of 2.0 to 7.0 mm ² / sec at 100 ° C. and a viscosity index of 200 or more, it can be used as it is or as a base oil of a lubricating oil composition at 100 ° C. from room temperature. Can be suitably used in a high temperature environment at least slightly above.

Claims (3)

Formula Ri Do from a compound or mixture of compounds represented by the formula (I), a 100 ° C. kinematic viscosity of 2.0~7.0mm ² / sec, synthetic lubricating oils Ru der viscosity index of 200 or more.
R ⁰ _n Si (OSiMe ₂ R ¹ ) _4-n (I)
(In the formula, R ⁰ is a phenyl group which may have an alkyl group having 1 to 3 carbon atoms and a substituent of a halogen atom , and Me is a methyl group. (4-n) R ^1s are , An aryl group, a linear or branched hydrocarbon group having 6 to 15 carbon atoms which may have a substituent of a halogen atom, and may be the same as or different from each other. 0 or 1) A lubricating oil composition containing the synthetic lubricating oil according to claim 1. A lubricating oil composition using the synthetic lubricating oil according to claim 1 as a base oil.