JPH0475895B2 - - Google Patents

Description

[Detailed Description of the Invention] [Industrial Field of Application] The present invention relates to a novel tetralin derivative useful as a traction drive fluid intermediate, lubricating oil, heat transfer oil, insulating oil, etc., a method for producing the same, and uses thereof. .

[Prior art and problems to be solved by the invention] In general, fluid for traction drive is used in traction drive devices (friction drive devices using rolling contact), such as automobile continuously variable transmissions, industrial continuously variable transmissions, It is a fluid used in hydraulic equipment, etc., and is required to have a high traction coefficient, stability against heat and oxidation, and economic efficiency.

In recent years, research has been focused on reducing the size and weight of traction drive devices, mainly for automotive applications, and along with this, the traction drive fluid used in these traction drive devices has also been developed to reduce the size and weight of traction drive devices, which can be used under various harsh conditions. In particular, it is required to be able to stably exhibit high performance over a wide temperature range from low to high temperatures (approximately -30 to 140 degrees Celsius).

Therefore, various compounds have been proposed in the past, including Japanese Patent Publications Nos. 46-338 and 46-339.
In terms of performance, it was still not satisfactory overall.

The inventors of the present invention have conducted extensive research in order to overcome the above-mentioned conventional drawbacks and develop a traction drive fluid that has a high traction coefficient from low to high temperatures, has an appropriate viscosity, and has excellent overall performance. Layered. In the course of this research, the present inventors discovered that a hydrogenated compound of 1-(1-tetralyl)-2-phenylpropane, which is one of the tetralin derivatives, has an excellent effect as a traction drive fluid. discovered that this 1-(1-tetralyl)-2-phenylpropane has excellent thermal stability and is useful as synthetic lubricating oil, heat transfer oil, etc., and based on this knowledge, completed the present invention. .

[Means for solving problems]

That is, the present invention first provides a novel tetralin derivative, 1-(1-tetralyl)-2-phenylpropane. The present invention also provides a second
Provided is a method for producing 1-(1-tetralyl)-2-phenylpropane, which comprises reacting tetralin with α-methylstyrene in the presence of a catalyst containing an alkali metal and/or an earth metal. It is something. Furthermore, thirdly, the present invention provides 1-
The present invention provides a synthetic lubricating oil containing (1-tetralyl)-2-phenylpropane as a main component.

The first new substance of the present invention, 1-(1-tetralyl)-2-phenylpropane, has the following structural formula [] It is expressed as

Although there are no particular restrictions on the method for producing 1-(1-tetralyl)-2-phenylpropane, it can be suitably produced, for example, according to the second aspect of the present invention.

In other words, the following structural formula [] Tetralin represented by and the following structural formula [] It can be obtained by reacting α-methylstyrene represented by the following in the presence of a catalyst containing an alkali metal and/or an alkaline earth metal. Here, the above-mentioned catalysts include alkali metals such as sodium (Na), potassium (K), lithium (Li), rubidium (Rb), beryllium (Be), magnesium (Mg), calcium (Ca),
Alkaline earth metals themselves such as strontium (Sr) can be used. Also, NaH,
Alkali (earth) metal hydrides such as KH, LiH, CaH ₂ , MgH ₂ , NaNH ₂ , KNH ₂ , Ca
Amides of alkali (earth) metals such as (NH ₂ ) ₂ , CH ₃ Li, C ₂ H ₅ Li, C ₃ H ₈ Li, C ₄ H ₁₀ Li,
_CH3Na , _{C2H5Na , C3H8Na , C4H10Na ,}
Alkylated products of alkali (earth) metals such as (CH ₃ ) ₂ Ca, C ₆ H ₅ Na, C ₆ H ₅ Li, C ₁₀ H ₇ Na,
Aryl compounds of alkali (earth) metals such as (C ₆ H ₅ ) ₂ Ca can be used alone or in combination. Also, during the reaction, potassium hydroxide,
Potassium carbonate, potassium t-butoxide, α-cumyl alcohol, cumene hydroperoxide, tetralin hydroperoxide, and the like can also be used as promoters.

In the method of the present invention, it is necessary to allow the reaction to proceed in the presence of such a catalyst, and the reaction temperature at this time is 20 to 200°C, preferably 50 to 150°C.
℃, and the molar ratio of tetralin and α-methylstyrene is the latter/former = 1/100 to 10,
It should preferably be selected in the range of 1/10 to 2. The amount of the catalyst used is 0.01 to 10 mol, preferably 0.05 to 3 mol, per mol of tetralin. In the method of the present invention, since the reaction is carried out under such conditions, the other raw material, α-methylstyrene, is selectively bonded to the α-position of the raw material, tetralin, and the 1- (1
-tetralyl)-2-phenylpropane is mainly obtained. Furthermore, according to the method of the present invention, since the reaction is carried out under the above conditions, compounds other than the above, such as 1-(2-tetralyl)-2-phenylpropane, 2-tetralyl-2-phenylpropane, etc. is hardly produced, and adducts of one molecule of tetralin and two molecules of α-methylstyrene, or adducts of two molecules of tetralin and one molecule of α-methylstyrene are also hardly produced.

Therefore, according to the method of the present invention, only the first compound of the present invention can be efficiently produced.

1-(1-tetralyl) thus obtained
-2-phenylpropane is preferably used as a synthetic lubricating oil because of its high thermal stability. The third aspect of the present invention relates to a synthetic lubricating oil containing this 1-(1-tetralyl)-2-phenylpropane as a main component.
In the third aspect of the present invention, mineral oil or other synthetic lubricating oil may be blended as necessary.

Furthermore, in the third aspect of the present invention, various additives may be used as appropriate. Specifically, for example, pour point depressants, viscosity index improvers, antifoaming agents, colorants, antioxidants, corrosion inhibitors, detergent dispersants, oiliness improvers, extreme pressure additives, rust preventives, and adhesives. ,
Examples include additives such as emulsifiers.

〔Effect of the invention〕

The hydrogenated compound of the novel tetralin derivative of the present invention has a high traction coefficient from low to high temperatures, and has an appropriate viscosity. Therefore, the novel tetralin derivatives of the present invention are useful as intermediates for traction drive fluids.

Further, the novel tetralin derivative of the present invention itself has excellent thermal stability. Therefore, it can be effectively used as turbine oil, bearing oil, internal combustion engine oil, gear oil, cutting oil, heat treatment oil, etc.

〔Example〕

Next, the present invention will be explained by examples.

Example 1 5 equipped with a stirrer, dropping funnel with gas inlet tube, reflux condenser with calcium chloride tube and thermometer
Tetralin 1452 was introduced into a four-necked glass flask while introducing argon gas through the gas introduction tube.
g (11.0 mol), metallic sodium 80 g (3.5 mol)
Then, 44.9 g (0.4 mol) of potassium t-butoxide was added as a promoter, and the mixture was heated to 125° C. in an oil bath. After stirring strongly for 1 hour to disperse the metallic sodium, 708 g of purified α-methylstyrene (6
A mixed solution of 132 g (1 mole) of Tetralin and Tetralin was added dropwise over 4 hours, and after the addition was completed, the reaction was completed by stirring for an additional hour. After cooling to room temperature, methanol 1 was added dropwise while stirring to decompose unreacted metallic sodium. After stopping the introduction of argon gas and washing the reaction mixture twice with 1 part of water,
It was washed once with a specified aqueous hydrochloric acid solution 1 and then twice with water 1. The oil layer was dried over anhydrous sodium sulfate and distilled under reduced pressure (165-168℃/0.2mmHg).
400 g (1.6 mol) of 1-(1-tetralyl)-2-phenylpropane with a purity of 90% was obtained. The purity was measured using a gas chromatograph equipped with a flame ionization detector (FID). In addition, the structure of 1-(1-tetralyl)-2-phenylpropane can be determined using a gas chromatograph/mass spectrometer (GC-MS), a proton nuclear magnetic resonance apparatus ( ^1H -NMR), and an infrared spectrophotometer (IR). It was decided. The properties of this product are shown below.

Refractive index (n ²⁰ _D ) 1.6595 Specific gravity (15/4℃) 1.0157 Kinematic viscosity 23.08cSt (40℃) 3.115cSt (100℃) Viscosity index -185 (based on JISK2284) Pour point -25.0℃ (based on JISK2269) Implementation Example 2 1-(1-
200 mg of 2-phenylpropane was purified using a high performance liquid chromatograph (manufactured by Nippon Waters Co., Ltd.) to obtain 1-(1-tetralyl)- with a purity of 97%.
120 mg of 2-phenylpropane was obtained. The purity was measured using a gas chromatograph equipped with a flame ion detector (FID). The results of this analysis are shown below.

Elemental analysis C ₁₉ H ₂₂ Calculated value (%) C: 91.1, H: 8.9 Actual value (%) C: 91.1, H: 9.0 Infrared absorption spectrum (manufactured by JASCO Corporation, A-
Type 3) As shown in Figure 1 Proton nuclear magnetic resonance spectrum (JEOL Ltd.)
(Nuclear Magnetic Resonance System GX-270)) As shown in Figure 2 Refractive index (n ²⁰ _D ) 1.5701 Example 3 1-(1-tetralyl)-2 obtained in Example 1
- A thermal stability test was conducted on phenylpropane at 170°C for 24 hours in accordance with JISK2540.

As a result, there was almost no change in the hue of the product before and after heating, and no sludge formation was observed, indicating that the product had excellent thermal stability.

Application example 1 In a 500 ml stainless steel autoclave with electromagnetic stirring, 90% pure 1-
(1-tetralyl)-2-phenylpropane 100g
and 3 g of a 5% by weight ruthenium-carbon catalyst (manufactured by Nippon Engelhard Co., Ltd.) and reacted at a hydrogen pressure of 30 atm and a temperature of 120°C. Nuclear hydrogenation proceeded completely in 2 hours, and 1-(1- Decalyl)-2
- Cyclohexylpropane was obtained quantitatively.
The relationship between the traction coefficient and temperature of this material is shown in FIG.

The traction coefficient was measured using a two-cylindrical friction tester. In other words, one of the adjacent cylinders of the same size (diameter 52 mm, thickness 6 mm, driven side is a tycoon type with a radius of curvature of 10 mm, and the driving side is a flat type without crowning) is set at a constant speed (1500 rpm), and the other is set at 1500 rpm. The cylinder was rotated continuously from 1,750 rpm to 1,750 rpm, a spring applied a load of 7 kg to the contact portion of both cylinders, the tangential force generated between the cylinders, that is, the traction force was measured, and the traction coefficient was determined. This cylinder is made of bearing steel SUJ-2 mirror finished and has a maximum Hertzian contact pressure of 112Kg.
It was f/ ^mm2 .

In addition, when measuring the relationship between traction coefficient and oil temperature, the oil temperature was varied from 40℃ to 140℃ by heating the oil tank with a heater.
This is a plot of the relationship between traction coefficient and oil temperature at a slip rate of 5%.

Comparative Example 1 5 equipped with a stirrer, dropping funnel with gas inlet tube, reflux condenser with calcium chloride tube and thermometer
1452 g of tetralin was introduced into a glass flask with argon gas introduced through the gas inlet.
(11.0 mol), sodium metal 80 g (3.5 mol) and potassium hydroxide 97 g as promoter
(1.7 mol) was added and heated to 135°C. 416 g (4.0 mol) of purified styrene and tetralin with stirring
132 g (1.0 mol) of the mixed solution was added dropwise over 3 hours while maintaining the temperature at 135-140°C. After the dropwise addition was completed, the mixture was heated and stirred for 1 hour, and then cooled to room temperature. After decomposing excess metal sodium by adding methanol little by little while stirring, the mixture was washed with saturated brine and 1N aqueous hydrochloric acid solution, and dried over anhydrous sodium sulfate. Separate the desiccant and perform vacuum distillation of the liquid to obtain a boiling point of 138-145℃/0.2mmHg fraction 400.
I got g.

Analysis of this fraction confirmed that it was 1-(1-tetralyl)-2-phenylethane. After putting 400 g of this fraction into a 1 volume autoclave, 15 g of 5 weight ruthenium-carbon catalyst (manufactured by Engelhard Japan) was added, and the hydrogen pressure was 50
Hydrogenation was carried out at Kg/cm ² G and reaction temperature of 170° C. for 4 hours. After cooling, the catalyst was filtered and the light components were stripped and analyzed, and the hydrogenation rate was 99.9% or more, which was found to be 1-(1-decalyl)-2-cyclohexylethane. The properties of this product are shown below. Moreover, the relationship between the traction coefficient and temperature of this material is shown in FIG.

Flexibility (n ²⁰ _D ) 1.5011 Specific gravity (15/4℃) 0.9336 Kinematic viscosity 27.48cSt (40℃) 4.204cSt (100℃) Pour point -35℃ or less (based on JISK2269) From Figure 3, the present compound 1 It can be seen that the nuclear hydride of -(1-tetralyl)-2-phenylpropane (Application Example 1) has a higher traction coefficient than the compound of Comparative Example 1, which has a similar molecular structure. Therefore, the compounds of the present invention are very useful as intermediates for traction drive fluids.

[Brief explanation of the drawing]

Figure 1 shows the 1-(1
Fig. 2 is an infrared absorption spectrum of -tetralyl)-2-phenylpropane, and Fig. 2 is its proton nuclear magnetic resonance spectrum. FIG. 3 is a graph showing the relationship between the traction coefficient of the fluid and the temperature in Application Example 1 of the present invention and Comparative Example 1.

Claims (1)

[Claims] 1 1-(1-tetralyl)-2-phenylpropane. 2. A method for producing 1-(1-tetralyl)-2-phenylpropane, which comprises reacting tetralin and α-methylstyrene in the presence of a catalyst containing an alkali metal and/or an alkaline earth metal. 3 A synthetic lubricating oil whose main component is 1-(1-tetralyl)-2-phenylpropane.