JPH0334794B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a power transmission medium made of hydrogenated substituted aromatic hydrocarbons. More specifically, the present invention relates to a power transmission medium using a hydrogenated aromatic hydrocarbon obtained by further hydrogenating a substituted aromatic hydrocarbon in which a tricyclododekyle group is substituted with a nuclear hydrogen atom. [Background of the Invention] The present inventor has discovered that tricyclo[5.2.1.0 ^2,6 ]deca-3
In the course of research on derivatives of aromatic hydrocarbons using -enes, the reaction product of the tricyclo[5.2.1.0 ^2,6 ]dec-3-enes and aromatic hydrocarbons is further hydrogenated. As a result, the present inventors have discovered that novel hydrogenated aromatic hydrocarbons can be obtained, and that these hydrogenated aromatic hydrocarbons are extremely useful as power transmission media, leading to the completion of the present invention. [Summary of the Invention] Therefore, the present invention provides aromatic hydrocarbons in which at least one nuclear hydrogen atom is a lower alkyl-substituted or unsubstituted tricyclo[5.2.1.0 ^2,6 ]dec-3-yl group. [] or tricyclo [5.2.1.0 ^2,6 ] deca-
The present invention relates to the use of hydrogenated substituted aromatic hydrocarbons which are hydrogenated products substituted with a 4-yl group [ ].

【formula】

[Manufacturing raw materials]

The aromatic hydrocarbons that are raw materials for producing one of the hydrogenated aromatic hydrocarbons used in the present invention include:
Usually has 6 to 14 carbon atoms, preferably 6 to 9 carbon atoms
and does not have an unsaturated group in the side chain,
For example, benzene, naphthalene, anthracene, and various alkyl group substituted products thereof, specifically toluene, o-xylene, m-ethyltoluene, p-ethyltoluene, n-butylbenzene, isobutylbenzene, sec-butyl benzene,
t-butylbenzene, various diethylbenzenes, 1
-Methylnaphthalene, 2-methylnaphthalene, 9
-Methyl anthracene, etc. can be mentioned. Other aromatic hydrocarbons used in the present invention include biphenyl, terphenyl, indane, and the like. Among these aromatic hydrocarbons, benzene and mono- or dialkyl-substituted benzenes are preferred, especially toluene, ethylbenzene and xylene. The tricyclo[5.2.1.0 ^2,6 ]dec-3-ene represented by the following general formula [] to be reacted with at least one of these aromatic hydrocarbons is preferably unsubstituted, but other 1st place, 7~
Those in which the 10th or 2nd to 6th positions are substituted with at least one lower alkyl group, such as a methyl group, ethyl group, propyl group, isopropyl group, or butyl group, are used. Substitution positions of the lower alkyl group include, for example, monosubstitution at the 3- to 10-positions excluding the 6-position, the 5,7-position, the 5,8-position, the 5,9-position,
- position, 5th, 10th position, 4th, 7th position, 4th, 8th position,
4,9-position, 3,8-position, 3,9-position, 1,4-position
Examples include di-substituted derivatives such as positions. (However, R ¹ , R ² , n, m: The same as the above definitions.) Such tricyclo[5.2.1.0 ^2,6 ]dec-3-ene is described, for example, in Japanese Patent Publication No. 11818/1981. It can be obtained by selectively hydrogenating dicyclopentadienes, as shown in FIG. When used in the present invention, it is preferable that this substance be pure, but it can be used as long as it has a purity of about 60% by weight or more; Contains polymerizable components such as partially hydrogenated products of ^2,6 ]dec-8-ene and cyclopentadiene oligomers (dimer or higher) and non-polymerizable components such as tricyclo[5.2.1.0]decane or its derivatives. Good too. [Production of substituted aromatic hydrocarbons] The reaction is carried out using tricyclo[5.2.1.0 ^2,6 ]deca in an amount of about 1 to 50 times, preferably about 1.2 to 10 times, in molar ratio to the aromatic hydrocarbons. Using -3-ene, pentane, hexane, heptane, dichloromethane, ethyl chloride, 1,2-dichloroethane,
It is carried out using a Friedel-Crafts type catalyst in the coexistence of a reaction solvent such as chlorobenzene. As a Friedel-Crafts type catalyst, for example,
_AlCl3 , _AlBr3 , _BF3 , _SnCl4 , _SnBr4 , _FeCl3 ,
BeCl ₂ , CdCl ₂ , ZnCl ₂ , BEl ₃ , BBr ₃ , TiCl ₄ ,
Lewis acids such as TiBr ₄ , ZrCl ₄ , and alkyl aluminum dichlorides; complexes of Lewis acids such as complexes of BF ₃ with alcohols, phenols, and ethers; and ternary complexes of AlCl ₃ with aromatic hydrocarbons and hydrogen halides are used. Among them, BF ₃ , AlCl ₃ or complexes thereof are preferably used. The amount of these catalysts used varies depending on the type of catalyst, the type and purity of both reaction raw materials, reaction temperature, etc., but in general, it is approximately 1.5% per aromatic hydrocarbon as a reaction raw material.
It is used in a proportion of ~50 mol%. The reaction is generally carried out at a temperature of about -10 to 200°C, preferably about 0 to 150°C, under normal pressure or pressurized conditions.
It lasts about 1 to 10 hours. As for the order of operation, first, both the reaction raw materials and the reaction solvent used as necessary are maintained at a predetermined temperature and pressure, and a catalyst is added while stirring to start the reaction. After reacting for a predetermined period of time, the remaining catalyst is removed according to a conventional method, and unreacted components and reaction solvent are removed by distillation to obtain the desired novel substituted aromatic hydrocarbons. Note that tricyclo[5.2.1.0 ^2,6 ]dec-3-ene, which is used as a raw material, hardly polymerizes by itself, so the target substituted aromatic hydrocarbons can be obtained with relatively high purity. . [Production of hydrogenated substituted aromatic hydrocarbons] The hydrogenated substituted aromatic hydrocarbons that are the substances used in the present invention are produced by hydrogenating the benzene nucleus contained in the structure of the substituted aromatic hydrocarbons. be able to. Hydrogenation is carried out using a solvent in the presence of a suitable hydrogenation catalyst. Catalysts include metals of groups and groups of the Periodic Table or their compounds, such as nickel, chromium, palladium, platinum, cobalt, osmium, rhenium, ruthenium, Raney nickel, nickel sulfide, nickel oxide, copper chromite, cobalt molybdenum sulfide, Molybdenum, platinum oxide, cobalt oxide, rhenium oxide, ruthenium oxide, sponge iron, iron oxide, etc. are used. In addition, various solvents can be used, such as pentane, hexane, heptane,
Various aliphatic and alicyclic solvents such as isoheptane, octane, isooctane, cyclohexane, methylcyclohexane, and decalin are used. Furthermore, if the substituted aromatic hydrocarbon has a low viscosity in liquid form at a predetermined reaction temperature, it can be directly hydrogenated without a solvent. Hydrogenation can be done by batch method or continuous method.
Usually at a temperature of 20 to 300°C, preferably about 100 to 240°C, under reduced pressure to increased pressure, generally atmospheric pressure to about 300 Kg/cm ² G, preferably about 10 to 150 Kg/cm ²
The treatment is carried out by treating with hydrogen gas under a pressure condition of G for about 10 minutes to about 24 hours, preferably about 10 minutes to about 24 hours, preferably about 10 minutes to about 7 hours. After hydrogenation, the solvent, unhydrogenated substituted aromatic hydrocarbons, and hydrogenated substituted aromatic hydrocarbons can be separated by a conventional method such as distillation. However, when hydrogenated substituted aromatic hydrocarbons are used as additives for adhesives as described below, it is not necessary to separate the unhydrogenated substituted aromatic hydrocarbons, and the two may be used as a mixture. can. in this case,
The total hydrogenation rate of the mixture is preferably 10% or more, particularly preferably 40% or more. [Substances Used in the Present Invention] Preferred novel hydrogenated substituted aromatic hydrocarbons obtained in this manner can be shown, for example, by the following general formula []. However, a tricyclo[5.2.1.0 ^2,6 ]dec-3-yl group or a tricyclo[5.2.1.0 ^2,6 ]dec-4-yl group (both are lower alkyl substituted or unsubstituted),
It is simply abbreviated as X. (In the formula, R is a lower alkyl group, S is an integer of 1 to 3, and when X is 2 or more, they are in the meta position with each other, and t is an integer of 1 to 2.) Hereinafter, the general formula [] Examples of substances of the present invention include those represented by:

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【formula】 [Power transmission medium]

The novel hydrogenated substituted aromatic hydrocarbon A used in the present invention has excellent properties as a power transmission medium in various mechanical devices. Special Publication No. 53-36105, Special Publication No. 46-338, Special Publication Showa
As described in publications such as No. 46-339 and Japanese Patent Publication No. 47-35763, various materials are used as power transmission media for various devices. As described in these publications, there are various characteristics required for a power transmission medium, but the medium used in a variable speed power transmission system that uses a traction drive or a traction friction clutch, that is, a traction Taking oil as an example, it is required to prevent wear and seizure of the contact portion between the driving side and the driven side, and to transmit power efficiently. A traction coefficient _t (= traction (frictional force)/normal load) is used as an index of such power transmission efficiency, and a vehicle with a high coefficient is desired. By using a lubricating oil (traction oil) with a high traction coefficient, the traction is large, which contributes to reducing fuel consumption in automobiles, etc., and the normal load is small, which leads to extending the life of the transmission. A used in the present invention has a high traction coefficient and is excellent as a power transmission medium. A used in the present invention may be used alone or in combination of two or more types. Among A used in the present invention, particularly preferable ones include X in the cyclohexane ring,
Examples include those in which one Y or Z is bonded, or those in which one X, Y or Z is bonded to a methylcyclohexane ring. The power transmission medium using A of the present invention may consist only of A, but other lubricating oils may be added to satisfy various required properties and functions, and additions that are usually added may also be used. agents, such as antioxidants,
Dispersants, metal deactivators, viscosity index improvers, anti-wear agents, rust inhibitors, corrosion inhibitors, foam inhibitors, seal swellers, friction modifiers, and the like may be included. The performance of A of the present invention as a power transmission medium will be shown in Examples below. In the Examples, the general properties of A were evaluated by the following method. (1) Softening point JIS K-5665 (2) Hue ASTM D 1544-58T Displayed by Gardner number (G.No.). (3) Molecular weight measured by field desorption ionization mass spectrometry. (4) Refractive index Measured at 25°C using an Atsube refractometer. (5) Viscosity 25 by Vismetron manufactured by Shibaura System Co., Ltd.
Measured at °C. [Example] Reference Example 1 The _C5 fraction obtained by naphtha decomposition was heated at 150°C for 3 hours, and the cyclopentadiene contained therein was converted to dicyclopentadiene, resulting in pentane, 20.1% of pentenes, and 0.5% of benzene. %, dicyclopentadiene 72.1%, isoprene-cyclopentadiene codimer 4.8%, and cyclopentadiene oligomer 2.5%. In a metal autoclave, 100 parts by weight (1710 g) of this crude dicyclopentadiene and 4 parts by weight of a palladium-diameter tablet-shaped hydrogenation catalyst (C31-1A, manufactured by Toyo C.C.I.) were charged, and the reaction temperature was 50°C and hydrogen pressure. The hydrogenation reaction was carried out under the condition of 10 Kg/cm ² with stirring for 12 hours. The catalyst was removed by filtration and distilled to obtain 90 parts by weight of tricyclo[5.2.1.0 ^2,6 ]dec-3-ene (9,10-dihydrodicyclopentadiene) fraction. Gas chromatography analysis results indicate that pentanes
19.9%, tricyclo[5.2.1.0 ^2,6 ]dec-3-ene
70.9%, dicyclopentadiene 0.1% or less, isoprene-cyclopentadiene codimer hydrogenation reaction product 4.5%, tricyclo[5.2.1.0 ^2,6 ]decane 2.1%, and unknown components 2.6%. Reference Example 2 195 g (2.5
mol) and 2 g of powdered anhydrous aluminum chloride are added under a nitrogen atmosphere. 94.5 g (0.5 mol) of a tricyclo[5.2.1.0 ^2,6 ]dec-3-ene-containing fraction (obtained in Reference Example 1 with a purity of 70.9%. The same applies to subsequent examples) from the dropping funnel while stirring. Add
Heat and stir at 70°C for 2 hours. The reaction was terminated by adding methanol, and the reaction solution was washed until it became neutral. Then, the mixture was distilled to obtain 12.5 g of an almost colorless distillate at a top temperature of 150 to 155° C. and a pressure of 5 mmHg. Molecular weight 212 (theoretical value 212 as the formula below), tricyclo [5.2.1.0 ^2,6 ] from the infrared stent (shown in Figure 1)
It turned out to be dec-4-ylpenzene.
The refractive index (n ²⁵ _D ) was 1.5558. Reference example 3 400 g of toluene in a four-necked flask with temperature diameter, stirring agent, condenser, and dropping funnel with a capacity of 1 mold release agent.
(4.35 mol) and 5 g of powdered anhydrous aluminum chloride are added under nitrogen atmosphere. Add tricyclo[5.2.1.0 ^2,6 ]deca-3- from the dropping funnel while stirring.
Ene-containing fraction (purity 70.9%) 126.9g (0.67mol)
was added dropwise and reacted at 70°C for 5 hours. The reaction was terminated by adding methanol, and the mixture was washed with water. The reaction solution was distilled to produce a colorless distillate with a boiling point of 158-162℃/5mmHg.
I got g. Molecular weight 226 (theoretical value 226 as the following formula),
Infrared spectroscopy and liquid chromatography revealed that it was a mixture of 2-, 3-, and 4-tricyclo[5.2.1.0 ^2,6 ]dec-4-yltoluene. The refractive index (n ²⁵ _D ) was 1.5582. Reference example 4 461g of ethylbenzene in the same equipment as reference example 3
(4.35 mol) and 5 g of powdered anhydrous aluminum
is added under nitrogen atmosphere. While stirring, 126.6 g (0.67 mol) of a tricyclo[5.2.1.0 ^2,6 ]dec-3-ene-containing fraction (purity 70.9%) was added through the dropping funnel, and the mixture was heated and reacted at 60°C for 2 hours. The reaction was terminated by adding methanol, and the reaction solution was washed until it became neutral. Then distilled, boiling point 170-174℃/5mm
115 g of Hg fraction was obtained. Molecular weight 240 (theoretical value 240 as the following formula), 2- and 3-
and 4-tricyclo[5.2.1.0 ^2,6 ]dec-4-yl-ethylbenzene. Reference Example 5 Mixed xylene (m-xylene) was added to the apparatus of Reference Example 2.
3 g of powdered anhydrous aluminum chloride are added to 79.5 g (0.75 mol) of 45% ethylbenzene, 51% ethylbenzene, 4% o- and p-xylene under a nitrogen atmosphere.
While stirring, add the tricyclo[5.2.1.0 ^2,6 ]dec-3-ene-containing fraction (purity 70.9) from the dropping funnel.
%) 283.5g (1.5 mol) was added, and the mixture was heated and stirred at 60°C for 2 hours. The reaction was terminated by adding methanol, and the reaction solution was washed until medieval times. Next, unreacted substances were removed at a pot temperature of 150°C and a pressure of 20 mmHg, and the Gardner hue was 10, the viscosity at 25°C was 10800 cp, and the refractive index (n ²⁵ _D ).
49 g of a viscous liquid of 1.5482 was obtained. As a result of analysis, tricyclo[5.2.1.0 ^2,6 ]dec-3-ene: 59% by weight of 1/1 adduct of mixed xylene, 39% by weight of 2/1 adduct of mixed xylene,
It was found that the rest consisted of 8% by weight. Example 1 34 g of tricyclo[5.2.1.0 ^2,6 ]dec-4-ylbenzene obtained in Reference Example 2, 118 g of Mitsui hexane (manufactured by Mitsui Petrochemical) and a sulfur-resistant nickel catalyst (manufactured by Nikki Chemical) as a hydrogenation catalyst. "N-113B") 2.5
g was placed in a 500 ml steel autoclave, and hydrogenation was carried out at a reaction temperature of 200° C., a reaction pressure of 40 Kg/cm ² G, and a reaction time of 5 hours. After cooling, depressurizing, and purging with nitrogen, the catalyst was filtered off, the filtrate was distilled, and the top temperature was 144-150℃.
33 g of colorless distillate was obtained at a pressure of 7 mmHg. molecular weight
218 (theoretical value 218 as the following formula), tricyclo [5.2.1.0 ^2,6 ] from the infrared spectrum (shown in Figure 2), etc.
It turned out to be dec-4-ylcyclohexane. The refractive index (n ²⁵ _D ) was 1.5110. Example 2 2-, 3- and 4- obtained in Reference Example 3
A mixture of 80 g of tricyclo[5.2.1.0 ^2,6 ]dec-4-yltoluene was added to the first
Hydrogenation reaction was carried out under the conditions shown in the table. After hydrogenation,
The catalyst was filtered off, and the filtrate was distilled at a top temperature of 154-158°C and a pressure of 7 mmHg to obtain 78 g of a colorless distillate. From the molecular weight of 232 (theoretical value of 232 as shown in the following formula), it was found to be a mixture of 2-, 3-, and 4-tricyclo[5.2.1.0 ^2,6 ]dec-4-ylmethylcyclohexane. The refractive index (n ²⁵ _D ) was 1.5080. Example 3 2-, 3- and 4- obtained in Reference Example 4
A mixture of tricyclo[5.2.1.0 ^2,6 ]dec-4-yl-ethylbenzene was hydrogenated in the same manner as in Example 1 under the conditions listed in Table 1. After hydrogenation, the catalyst was filtered off, and the filtrate was heated to a top temperature of 163-168℃.
Distillation was carried out at a pressure of 7 mmHg to obtain 98 g of a colorless distillate.
2 from the molecular weight 246 (theoretical value 246 as the following formula) etc.
- and 3- and 4-tricyclo[5.2.1.0 ^2,6 ]
It was found to be mainly a mixture of dec-4-yl-ethylcyclohexane. Example 4 Tricyclo[5.2.1.0 ^2,6 ]dec-3-ene obtained in Reference Example 5: 59% by weight of 1/1 adduct of mixed xylene, 33% by weight of 2/1 adduct of mixed xylene, and 8% by weight of other % was subjected to a hydrogenation reaction in the same manner as in Example 1 under the conditions listed in Table 1. After hydrogenation, the catalyst was filtered off, and the solvent was removed from the filtrate at a pot temperature of 150°C and a pressure of 20 mmHg. At 25°C, the viscosity was 10,600 cp, and the refractive index (n ²⁵ _D )
39 g of 1.5028 viscous liquid were obtained. As a result of analysis, tricyclo[5.2.1.0 ^2,6 ] deca-3
-Ene: 1/1 addition hydrogenated product of mixed xylene 59% by weight,
It was found that it consisted of 33% by weight of the 2/1 adduct and 8% by weight of other substances.

【table】

[Table] Examples 5 to 8, Comparative Examples 1 to 3 Regarding the new hydrogen-substituted aromatic hydrocarbons obtained in Examples 1 to 4, boiling points, viscosity, pour points, and traction coefficients as Examples 5 to 8, respectively. are shown in Table 2. As a comparative example, Comparative Example 1 contains 2-methyl-2,4-dicyclohexylpentane obtained by hydrogenating α-methylstyrene linear dimer, Comparative Example 2
The properties of hydrogenated polybutene (Polybutene OH, manufactured by Idemitsu Petrochemical Industries) were listed for Example 3, and the properties of naphthenic mineral oil (Ciel Flex 371JY, manufactured by Shell Chemical) were listed for Comparative Example 3. The evaluation method is as follows. Viscosity: E-type viscometer manufactured by Tokyo Keiki Co., Ltd. Pour point: JIS K-2269 Traction coefficient: Traction coefficient (t) at a rotational speed of 1200 rpm was determined from the following formula using an incometer (B45 type) manufactured by Toyo Seiki Co., Ltd. t=Ft/Pn where, Ft: Traction, Pn: Normal load (2500g)

[Table] As can be seen from the table, A used in the present invention is useful as a power transmission medium, particularly as a traction oil.

[Brief explanation of drawings]

FIG. 1 and FIG. 2 show infrared absorption spectra of the reaction products obtained in Example 1 and Example 2, respectively, with the horizontal axis representing the wave number.

Claims (1)

[Scope of Claims] 1. At least one nuclear hydrogen atom of aromatic hydrocarbons is a lower alkyl substituted or unsubstituted tricyclo[5.2.1.0 ^2,6 ]dec-3-yl group or tricyclo[5.2.1.0 ^{2 ,6} ] A power transmission medium comprising a hydrogenated aromatic hydrocarbon substituted with a dec-4-yl group.