JP2608305C - - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a traction drive fluid, and more particularly, to a traction drive fluid having low viscosity and excellent traction performance over a wide temperature range from low to high temperatures. . [Problems to be Solved by Related Art and Invention] Generally, a traction drive fluid is a traction drive device (friction drive device by rolling contact), such as a continuously variable transmission for automobiles, a continuously variable transmission for industrial use, hydraulic equipment, and the like. It is a fluid used for high-performance liquids, and is required to have a high traction coefficient, stability against heat and oxidation, economy, and the like. By the way, the size of the traction drive device is said to be inversely proportional to the traction coefficient of the traction drive fluid used to the 0.45th power.The more the traction drive fluid with the lowest traction coefficient in the operating temperature range is used, the more the traction drive fluid is used. It is said that the device can be downsized. In recent years, reductions in the size and weight of traction drive devices have been studied mainly for automotive applications, and accordingly, traction drive fluids used in this traction drive device can withstand use under various severe conditions. Demonstrate high performance (especially high traction coefficient, low viscosity, excellent heat and oxidation stability, etc.) over a wide temperature range from low temperature to high temperature (about -30 to 140 ° C). Is required. However, various traction drive fluids have been developed, such as Japanese Patent Publication Nos. 46-338 and 46-339, but none of them can satisfy the above-mentioned required characteristics. There were various problems. For example, a compound exhibiting a high traction coefficient at a high temperature has a high viscosity and a large stirring loss, so that the transmission efficiency is low, and there is also a problem in low-temperature startability. On the other hand, a compound having a low viscosity and excellent transmission efficiency has a low traction coefficient at a high temperature, and also has a too low viscosity at a high temperature, which causes trouble in lubrication of a traction transmission device. [Means for Solving the Problems] Accordingly, the present inventors have solved the above-mentioned problems of the conventional technology and developed a traction drive fluid having low viscosity and excellent performance over a wide temperature range from low to high temperatures. I did my best research. As a result, by polymerizing dicyclopentadiene or dihydrodicyclopentadiene, and further hydrogenating it, a polymer hydrogenated product having a weight average molecular weight of 250 or more is blended with another traction oil to achieve the intended purpose. It has been found that a traction drive fluid having traction performance can be obtained. The present invention has been completed based on such findings. That is, the present invention relates to a hydrogenated polymer of dicyclopentadiene and / or dihydrodicyclopentadiene having a weight average molecular weight of 250 or more.
A traction drive fluid characterized by being contained in traction oil in a range of 60% by weight. The polymer hydrogenated product in the present invention is obtained by polymerizing one or both of dicyclopentadiene (DCPD) and dihydrodicyclopentadiene (DHDCPD) as a raw material, and further hydrogenating the polymer. In the polymerization of DCPD and / or DHDDCPD, 2
Thermal polymerization may be performed at a temperature of 00 ° C. or higher, or polymerization may be performed in the presence of a catalyst. Further, these polymerizations can be carried out using a solvent, if necessary. Various catalysts can be used as the catalyst used for the polymerization of DCPD and DHDDCPD, but an acidic catalyst is generally used. Specifically, clays such as activated clay and acid clay, mineral acids such as sulfuric acid, hydrochloric acid and hydrofluoric acid, organic acids such as p-toluenesulfonic acid and triflic acid, aluminum chloride, ferric chloride and chloride Lewis acids such as stannic, boron trifluoride, boron tribromide, aluminum bromide, gallium chloride, gallium bromide, and solid acids such as zeolites, silica, alumina, silica-alumina, cation exchange resins, heteropoly acids And the like can be used, but may be appropriately selected in consideration of ease of handling, economy, and the like. The amount of use is not particularly limited, but is usually in the range of 0.1 to 100% by weight, preferably 1 to 20% by weight, based on the DCPD or DHDCPD. In the above polymerization, a solvent is not necessarily required, but it is preferable to use a solvent in handling the polymerization raw material or catalyst during the reaction or for controlling the progress of the reaction. As such a solvent, almost any saturated hydrocarbon such as n-pentane, n-hexane, heptane, octane, nonane, decane and the like, and cyclopentane, cyclohexane, methylcyclohexane and decalin can be used. , Xylene and other aromatic hydrocarbons, tetralin and the like can also be used. The conditions of such a polymerization reaction may be appropriately selected according to various situations, and cannot be unambiguously determined, but are usually appropriate in a temperature range of −30 to 300 ° C. depending on the type of the catalyst, additives, and the like. The conditions are set. For example, when the catalyst is clay or zeolite, the reaction temperature is from room temperature to 300 ° C., preferably 60 ° C. or higher, and when the other catalyst is used, the reaction is performed at −30 to 100 ° C., preferably 0 to 60 ° C. Will be Next, the thus obtained polymer (including copolymer) of DCPD or DHDCPD is hydrogenated (hydrogenated) to obtain a target polymer hydrogenated product. The hydrogenation may be performed on the entire amount of the above-mentioned polymer, or may be performed by fractionating or fractionating a part thereof. This hydrogenation is generally performed in the presence of a catalyst, and the catalyst may include one or more metals such as nickel, ruthenium, palladium, platinum, rhodium, iridium, copper, chromium, molybdenum, cobalt, and tungsten. What is known as a so-called hydrogenation catalyst can be used. The amount of the catalyst added is in the range of 0.1 to 100% by weight, preferably 1 to 10% by weight, based on the polymer. The hydrogenation proceeds in the absence of a solvent as in the case of the above-mentioned polymerization reaction, but a solvent can be used. In this case, n-pentane, n-hexane, heptane, octane, nonane , Decane, dodecane, etc., and most liquid saturated hydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane and the like can be used. Further aromatics, olefins or alcohols, ketones,
Any liquids such as ethers can be used, but saturated hydrocarbons are particularly preferable. The reaction temperature is usually from room temperature to 300 ° C., preferably from 40 to 200 ° C., and the reaction pressure can be from normal pressure to 200 kg / cm ² G, preferably from normal pressure to 100 kg / m ² G. It can be performed by the same operation as general hydrogenation. The polymer hydrogenated product of DCPD and / or DHDCPD thus produced must have a weight average molecular weight of 250 or more, preferably 2
It is 50 to 4000, particularly preferably 250 to 1300. When the weight average molecular weight is less than 250, high traction performance cannot be exhibited. The above-mentioned polymer hydrogenated product has a different viscosity depending on the degree of polymerization, but generally has a high viscosity, so that it is used for blending with another traction oil to improve its traction coefficient. In this case, the amount of the polymer hydrogenated compound may be appropriately selected depending on the type of the polymer hydrogenated product, the type of other traction oil to be blended, and the like. 2 to 60% by weight, preferably 5
It is determined in the range of ６０60% by weight. Further, other traction oils to be blended with the above-mentioned polymer hydrogenated product include various oils such as those conventionally used as traction drive oils and oils that have low traction performance alone and are not practically used. I can give it. For example, mineral oils such as paraffinic mineral oil, naphthenic mineral oil, intermediate mineral oil, alkylbenzene, polybutene, polyα-olefin, synthetic naphthene, ester, ether, etc.
A very wide range of liquids can be raised. Among them, alkylbenzene, polybutene and synthetic naphthene are preferred. Here, examples of the synthetic naphthene include an alkane derivative having two or three or more cyclohexane rings, an alkane derivative having one or more decalin rings and one or more cyclohexane rings, an alkane derivative having two or more decalin rings, a cyclohexane ring or a decalin ring. Are compounds having a structure in which two or more are directly bonded. Specific examples of such synthetic naphthenes include 1-cyclohexyl-1-decalylethane; 1,3-dicyclohexyl-3
-Methylbutane; 2,4-dicyclohexylpentane; 1,2-bis (methylcyclohexyl) -2-methylpropane; 1,1-bis (methylcyclohexyl)
2-methylpropane; 2,4-dicyclohexyl-2-methylpentane; limonene dimer hydrogenation; pinene dimer hydrogenation; camphene dimer hydrogenation. The fluid for traction drive of the present invention is DCPD and / or DHDCP.
It contains a polymer hydrogenated product of D as an essential component, and is further prepared by blending another liquid substance (traction oil). In addition, if necessary, an antioxidant, a rust inhibitor, a cleaning dispersant, a fluid Various additives such as a point depressant, a viscosity index improver, an extreme pressure agent, an anti-wear additive, an anti-fatigue agent, an antifoaming agent, an oiliness improver, and a colorant can be used in an appropriate amount. EXAMPLES Next, the present invention will be described in more detail with reference to Examples and Comparative Examples. Comparative Example 1 552 g of toluene and 27.6 g of anhydrous aluminum chloride were placed in a two-liter four-necked flask.
g and 12.6 g of nitromethane were added, and 181.2 g of methallyl chloride was added dropwise over 2 hours while stirring at 0 ° C., and stirring was continued for 1 hour to complete the reaction. After adding 75 ml of water to decompose aluminum chloride and separating an oil layer, the oil layer was washed with 200 ml of water once and 300 ml of 1N aqueous sodium hydroxide solution.
, And dried over anhydrous magnesium sulfate. Next, unreacted raw materials were distilled off by a rotary evaporator, followed by distillation under reduced pressure to obtain 254 g of a fraction having a boiling point of 114 to 116 ° C / 0.14 mmHg. As a result of the analysis, this fraction was found to be 80% 2-methyl-1,2-ditolylpropane and 20% 2-isomer-1,2-methyl-1,1-ditolylpropane. Subsequently, 250 g of this fraction was put into a 1-liter autoclave, 20 g of a nickel catalyst (N-113, manufactured by Nikki Chemical Co., Ltd.) was added, and the hydrogen pressure was 70 kg / cm ² G and the temperature was 180 °.
Hydrogenation was performed at 5 ° C. for 5 hours. When the catalyst was removed from the obtained reaction product and analyzed, the hydrogenation rate was 99.9% or more, 2-methyl-1,2-di (methylcyclohexyl) propane was 80%, and 2-methyl- The 1,1-di (methylcyclohexyl) propane was found to be 20%. The properties of this product were as follows. Kinematic viscosity 13.17 cSt (40 ° C.) 2.622 cSt (100 ° C.) Viscosity index −30 Specific gravity (15/4 ° C.) 0.8824 Pour point −47.5 ° C. Refractive index (n _D ) 1.4800 The traction coefficient of the object was measured in the temperature range from 60 ° C to 140 ° C. The result is shown in FIG. Example 1 A commercially available hydrogenated petroleum resin (weight average molecular weight: 540, manufactured by Exxon Chemical Co., Ltd., trade name: dicyclopentadiene (DCPD)) was added to the fluid obtained in Comparative Example 1 above. ESCOREZ 5300) was mixed at 10% by weight to obtain a fluid. The properties of this fluid were as follows. Kinematic viscosity 23.15cSt (40 ℃) 3.686cSt (100 ℃) Viscosity Index -24 specific gravity (15/4 ℃) 0.8991 Pour point -37.5 ° C. refractive index (n _D) 1.4861 Further, the fluid Was measured in the temperature range of 60 ° C to 140 ° C. The result is shown in FIG. Comparative Example 2 Ethylbenzene (2700 g) and metallic sodium (5) were placed in a glass flask having an inner volume of 5 l.
8 g and potassium hydroxide 16 g, and heated to 120 ° C. while stirring α-
A mixture of 1100 g of methylstyrene and 300 g of ethylbenzene was gradually dropped over 5 hours, and then stirred for 1 hour to carry out a reaction. After completion of the reaction, the reaction mixture was cooled to separate and collect an oil layer. To this, 200 g of methyl alcohol was added, and the mixture was washed three times with 2 l of a 5N hydrochloric acid aqueous solution and 2 l of a saturated saline solution.
Next, after drying over anhydrous sodium sulfate, unreacted ethylbenzene was distilled off by a rotary evaporator, and the residue was further distilled under reduced pressure to a boiling point range of 0.06 mmHg at 10 mmHg.
1350 g of a fraction at 6 to 108 ° C. was obtained. Next, 500 ml of this fraction was placed in an autoclave having an internal volume of 1 liter, and 20 g of a nickel catalyst for hydrogenation (N-113, manufactured by Nikki Chemical Co., Ltd.) was added.
And hydrogenation at a hydrogen pressure of 50 kg / cm ² G. After the reaction, remove the catalyst,
As a result of stripping and analyzing the light components, the hydrogenation rate was 99.9% or more, and it was confirmed that the hydrogenated product was 2,4-dicyclohexylpentane. The properties of this product were as follows. Kinematic viscosity 12.05 cSt (40 ° C.) 2.750 cSt (100 ° C.) Viscosity index 47 Specific gravity 0.8913 Refractive index (n _D ) 1.4832 Pour point -50 ° C. or less Further, the traction coefficient of this product is reduced from 60 ° C. The measurement was performed in a temperature range of 140 ° C., and the results are shown in FIG. Example 2 The fluid obtained in Comparative Example 2 was mixed with 10% by weight of the hydrogenated petroleum resin used in Example 1 to obtain a fluid. The properties of the obtained fluid were as follows. Kinematic viscosity 19.89 cSt (40 ° C.) 3.736 cSt (100 ° C.) Viscosity index 52 Specific gravity 0.9074 Refractive index (n _D ) 1.4899 Pour point −47.5 ° C. Further, the traction coefficient of this fluid is 60 ° C. From 140 ° C. to 140 ° C., and the results are shown in FIG. Example 3 500 g of DCPD and 8 g of a developed Raney cobalt catalyst were placed in a 1-liter stainless steel autoclave, and hydrogenated at a hydrogen pressure of 10 kg / cm ² G and 100 ° C. for 1 hour. After cooling, the catalyst was filtered and analyzed. DHDDCPD 92%, DCPD
About 500 g of a liquid of 2% and 6% of tetrahydrodicyclopentadiene were obtained. Next, a Dimroth reflux condenser and a thermometer were attached to a 1-liter three-necked flask.
500 g of the above-mentioned liquid containing DHDCPD as a main component and 100 g of dried activated clay were added and stirred at 150 ° C. for 10 hours. After filtration of the activated clay from the reaction mixture, unreacted DHDDCPD was distilled off, the mixture was placed in a 1-liter stainless steel autoclave, and hydrogen pressure was 10 kg with a nickel / diatomaceous earth catalyst (N-113, manufactured by Nikki Chemical Co., Ltd.).
/ Cm ² G, hydrogenated at 150 ° C. to obtain about 200 g of a polymer hydrogenated product (weight average molecular weight: 320) of a dimer or more of DHDCPD. This polymer hydrogenated product was mixed with the fluid obtained in Comparative Example 1 at 10% by weight. Its properties were as follows. Kinematic viscosity 18.10 cSt (40 ° C.) 3.153 cSt (100 ° C.) Viscosity index −35 Specific gravity 0.8994 Refractive index (n _D ) 1.4862 Pour point −37.5 ° C. Further, the traction coefficient of this product is 60. The measurement was performed in a temperature range of from 140 ° C. to 140 ° C., and the results are shown in FIG. The measurement of the traction coefficient in Examples and Comparative Examples was performed using a two-cylinder friction tester. That is, one of the cylinders of the same size (52 mm in diameter, 6 mm in thickness, a die type having a radius of curvature of 10 mm on the driven side, and a flat type without crowning on the driven side) at a constant speed (1500 rpm) and the other at 1500 rpm From 1750
The cylinder was continuously rotated to rpm, a 7 kg load was applied to the contact portion between the cylinders by a spring, and the tangential force generated between the cylinders, that is, the traction force was measured, and the traction coefficient was determined. This cylinder was made of SUJ-2 mirror-finished bearing steel and had a maximum Hertzian contact pressure of 112 kgf / mm ² . In the measurement of the relationship between the number of traction systems and the oil temperature, the oil temperature was changed from 60 ° C. to 140 ° C. by heating the oil tank with a heater. This is a plot of the relationship with. [Effects of the Invention] As described above, the traction drive fluid of the present invention containing a polymer hydrogenated product of DCPD or DHDCPD has a high traction coefficient over a wide temperature range from normal temperature to high temperature, and improves transmission efficiency. . As a result, the size and weight of the traction drive device can be reduced, the life thereof can be extended, and the output can be increased, and the traction drive device can be widely used for various mechanical products such as a continuously variable transmission for automobiles or industries, and hydraulic equipment. Further, the above-mentioned polymer hydrogenated product can increase the traction coefficient only by blending it in a small amount with another fluid, and can provide various excellent traction drive fluids.

BRIEF DESCRIPTION OF THE DRAWINGS FIGS. 1 and 2 are graphs showing a change in temperature of a traction coefficient of a traction drive fluid obtained in Examples and Comparative Examples.

Claims (1)

Claims (1) Traction oil containing a hydrogenated polymer of dicyclopentadiene and / or dihydrodicyclopentadiene having a weight average molecular weight of 250 or more in a range of 2 to 60% by weight. A fluid for traction drive, characterized in that: