JP2888733B2 - Method for producing oligomer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an oligomer, and more particularly, to a hydrocarbon-based traction drive fluid having good low-temperature fluidity and excellent traction performance over a wide temperature range from low to high temperatures. The present invention relates to an efficient method for producing an oligomer to be provided.

[0002]

2. Description of the Related Art Generally, a traction drive fluid is a traction drive device (friction drive device by rolling contact), for example,
A fluid used in continuously variable transmissions for automobiles, continuously variable transmissions for industrial use, hydraulic equipment, and the like. As demand increases, a high traction coefficient, stability against heat and oxidation, economic efficiency, and the like are required. 2. Description of the Related Art In recent years, reductions in the size and weight of traction drive devices have been studied mainly for automotive applications. Accordingly, the traction drive fluid used in this traction drive device also has a performance that can withstand use under various severe conditions, especially from a low temperature to a high temperature (−30).
It is required to exhibit high performance (high traction coefficient, low viscosity, excellent heat and oxidation stability, etc.) stably over a wide temperature range up to about 140 ° C.). However, various traction drive fluids have been developed, including Japanese Patent Publication No. 46-338, Japanese Patent Publication No. 46-339, and Japanese Patent Publication No. 61-44918, all of which have the above-mentioned required characteristics. There was nothing that could be satisfied, and 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 remarkably low traction coefficient at a high temperature, and has a too low viscosity at a high temperature, which causes trouble in lubrication of a traction drive device.

In view of the above situation, the research group of the present inventors has studied to solve the problems of the conventional method, and as a result, it has found that an unsaturated bicycloheptane derivative oligomer hydride (Japanese Unexamined Patent Application Publication No. -95295
No. 3) and unsaturated bicyclooctane derivative oligomer hydride (Japanese Patent Application No. 3-75145) have excellent performance as traction drive fluids. Meanwhile, when producing the above-mentioned unsaturated bicycloheptane derivative oligomer hydride and unsaturated bicyclooctane derivative oligomer hydride, it is necessary to oligomerize the unsaturated bicycloheptane derivative and the unsaturated bicyclooctane derivative before hydrogenation. Here, the unsaturated bicycloheptane derivative and the unsaturated bicyclooctane derivative which are the raw materials of the oligomer are obtained by dehydration reactions of the corresponding alcohols. However, when the unsaturated bicycloheptane derivative and the unsaturated bicyclooctane derivative obtained by the dehydration reaction of the corresponding alcohol are oligomerized, if the cyclopentadiene derivative or the cyclohexadiene derivative which is a by-product of the dehydration reaction is present, the oligomerization is carried out. Did not progress smoothly.

[0004]

Means for Solving the Problems Accordingly, the present inventors have:
In order to solve the above-mentioned problems, we conducted intensive research. as a result,
When producing an unsaturated bicycloheptane derivative and an unsaturated bicyclooctane derivative by a dehydration reaction of a corresponding alcohol, the amount of by-product cyclopentadiene derivative and cyclohexadiene derivative is reduced to 1% or less and used as an oligomerization raw material. As a result, it was found that the oligomerization reaction proceeds smoothly. The present invention has been completed based on such findings. That is, in the present invention, when a raw material containing an unsaturated bicyclo [2.2.1] heptane derivative and / or an unsaturated bicyclo [2.2.2] octane derivative is oligomerized, the diene content in the raw material is reduced. An object of the present invention is to provide a method for producing an oligomer, characterized in that the content is 1% by weight or less.

First, in the present invention, the unsaturated bicyclo [2.2.1] heptane derivative in the raw material to be subjected to oligomerization is an unsaturated bicyclo [2.2.1] heptane and a derivative thereof. Although it may be produced by such a method, it is generally produced by a dehydration reaction of a corresponding alcohol, and is produced so that the production of diene as a decomposition by-product is 1% or less. Obtained by: Specifically, for example, bicyclo [2.2.
1] hept-2-ene; 2-methylenebicyclo [2.
2.1] heptane; 2-methylbicyclo [2.2.1]
Hept-2-ene: 2-methylene-3-methylbicyclo [2.2.1] heptane: 2,3-dimethylbicyclo [2.2.1] hept-2-ene; 2-methylene-7-
Methylbicyclo [2.2.1] heptane; 2,7-dimethylbicyclo [2.2.1] hept-2-ene; 2-methylene-5-methylbicyclo [2.2.1] heptane;
2,5-dimethylbicyclo [2.2.1] hept-2-
Ene; 2-methylene-6-methylbicyclo [2.2.
1] heptane; 2,6-dimethylbicyclo [2.2.
1] Hept-2-ene; 2-methylene-1-methylbicyclo [2.2.1] heptane; 1,2-dimethylbicyclo [2.2.1] hept-2-ene; 2-methylene-4
-Methylbicyclo [2.2.1] heptane; 2,4-dimethylbicyclo [2.2.1] hept-2-ene; 2-
Methylene-3,7-dimethylbicyclo [2.2.1] heptane; 2,3,7-trimethylbicyclo [2.2.
1] Hept-2-ene; 2-methylene-3,6-dimethylbicyclo [2.2.1] heptane; 2,3,6-trimethylbicyclo [2.2.1] hept-2-ene; 2-
Methylene-3-ethylbicyclo [2.2.1] heptane; 2-methyl-3-ethylbicyclo [2.2.1] hept-2-ene;

In the present invention, the unsaturated bicyclo [2.2.2] octane derivative in the raw material to be subjected to oligomerization is an unsaturated bicyclo [2.2.2] octane and a derivative thereof. Is an unsaturated compound obtained by a dehydration reaction of an alcohol derivative. Specifically, for example, bicyclo [2.2.2] oct-2-ene; 2-methylenebicyclo [2.2.2] octane;
-Methylbicyclo [2.2.2] oct-2-ene; 2
-Methylene-3-methylbicyclo [2.2.2] octane; 2,3-dimethylbicyclo [2.2.2] oct-
2-ene and the like.

These unsaturated bicyclo [2.2.1] heptane and its derivatives and unsaturated bicyclo [2.2.2]
Octane and its derivatives are usually obtained as follows. That is, first, a cyclodiene is reacted with an aldehyde or an alcohol. Next, after cooling, the reaction product is hydrotreated in the presence of a catalyst (for example, Raney nickel catalyst). Subsequently, after cooling, the catalyst is filtered off and the filtrate is distilled under reduced pressure to produce the corresponding alcohol derivative. Here, examples of the cyclodienes include cyclopentadiene, dimethylcyclopentadiene, methylcyclopentadiene, cyclohexadiene, methylcyclohexadiene and derivatives thereof. Here, examples of the derivative include dicyclopentadiene, methylcyclopentadiene dimer, and dimethylcyclopentadiene dimer.

On the other hand, aldehydes include, for example, crotonaldehyde, acrolein (acrylaldehyde) and the like. Also, as alcohols,
An example is allyl alcohol. In the present invention, these unsaturated bicyclo [2.2.1] heptane derivatives and unsaturated bicyclo [2.2.2] octane derivatives can be used as a mixture. In this case, the cyclodienes, the aldehydes and the alcohols may be used in combination, and the reaction may be performed in the same manner.

The corresponding alcohol obtained as described above is subjected to a dehydration reaction in the presence of a catalyst,
An unsaturated bicyclo [2.2.2] heptane derivative or an unsaturated bicyclo [2.2.2] octane derivative can be obtained. In addition, during the dehydration reaction, a cyclopentadiene derivative or a cyclohexadiene derivative is by-produced, so that its production needs to be 1% or less. Catalysts used for this dehydration reaction include alumina, titania,
Metal oxides such as chromia, magnesia and silica-alumina; metal phosphates such as calcium phosphate, zirconium phosphate and calcium hydroxyabatite; metal sulfates such as magnesium sulfate, calcium sulfate and aluminum sulfate; zeolites; bentonite and montmorillonite Any of layered silicates such as kaolin and kaolin may be used. Among them, γ-
Alumina is preferably used. When a dehydration reaction is performed using these catalysts, the reaction conditions cannot be unconditionally determined depending on the balance between the reaction temperature and the weight hourly space velocity (WHSV), but the reaction temperature is generally 50 to 400.
° C, preferably 100 to 350 ° C. Also, WHS
V is 0.1 to 10.0 hr ^-1 , preferably 0.5 to 5.0 hr
It is ^-1 . The unsaturated bicyclo [2,2,1] heptane derivative and the unsaturated bicyclo [2,2,1] octane derivative may be obtained under any reaction conditions, but dienes which are reaction by-products of the dehydration reaction Is essential to be 1% or less. Further, by precision distillation of the obtained olefin, the reaction by-product may be reduced to 1% or less.

As described above, the dehydration reaction or the unsaturated bicyclo [2.2.1] heptane derivative and / or the unsaturated bicyclo [2.2.2] which has been subjected to a dehydration reaction and then a distillation treatment.
Octane derivatives are oligomerized. The oligomer obtained by this oligomerization is then subjected to a hydrogenation reaction, and the hydrogenated oligomer is preferably provided to a traction drive fluid. Here, the oligomerization reaction of the starting olefin is carried out in the presence of a catalyst, if necessary, by adding a solvent or a reaction regulator. Although various catalysts can be used, an acid catalyst is generally used. Examples of the acid catalyst include clays such as activated clay and acid clay, mineral acids such as sulfuric acid and hydrochloric acid, organic acids such as p-toluenesulfonic acid and triflic acid, aluminum chloride, ferric chloride, stannic chloride, and the like. Titanium trichloride, titanium tetrachloride, boron trifluoride, hydrogen fluoride, boron tribromide, aluminum bromide,
Lewis acids such as gallium chloride and gallium bromide, and solid acids such as zeolite, silica, alumina, silica
Alumina, cation exchange resin, heteropoly acid (for example,
Although various substances such as phosphotungstic acid, phosphomolybdic acid, silicotungstic acid, silicomolybdic acid) can be used, they may be appropriately selected in consideration of ease of handling, economy, and the like. The amount used 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 raw materials such as bicyclooctane and bicycloheptanes.

In the above oligomerization and co-oligomerization reaction of the unsaturated bicyclo [2.2.1] heptane derivative and / or the unsaturated bicyclo [2.2.2] octane derivative, a solvent is not necessarily required. It is preferable to use these compounds in handling the bicycloheptanes or octanes or the like during the reaction or in controlling the progress of the reaction. As such a solvent, for example, a saturated hydrocarbon such as n-pentane, n-hexane, heptane, octane, nonane, decane or the like or cyclopentane, cyclohexane, methylcyclohexane, decalin or the like is widely used without any particular limitation. be able to. Further, when the catalyst is a catalyst having a weak reaction promoting property such as clay, aromatic hydrocarbons such as benzene, toluene and xylene, and tetralin can also be used. Further, mineral oil (150 neutral, 500 neutral, etc.) can be used.

The reaction modifier is used to make bicycloheptanes or octanes react appropriately, if necessary, especially to increase the selectivity of the oligomerization and co-oligomerization reactions. Is in the range of 0.1 to 100% by weight, preferably 0.5 to 20% by weight, based on the amount of catalyst used. Specific examples of the reaction modifier include carboxylic acids such as acetic acid; acid anhydrides such as acetic anhydride and phthalic anhydride; cyclic esters such as γ-butyrolactone and valerolactone; glycols such as ethylene glycol; Esters such as ethyl, ketones such as mesityl oxide, aldehydes such as formalin and acetaldehyde, cellosolve and water can be used.

The conditions for the above reaction are generally -30
Appropriate conditions are set depending on the type of the catalyst, the additive, and the like in the temperature range of ℃ to 300 ℃. For example, when the catalyst is clay or zeolite, the reaction temperature is from room temperature to 250 ° C., preferably 60 ° C. or higher, and the other catalyst is −30 ° C.
To 100 ° C, preferably 0 ° C to 60 ° C. At the time of the above-mentioned oligomerization and co-oligomerization reaction, a heavy component of trimer or more is by-produced, but is used as a viscosity modifier or a traction coefficient modifier by hydrogenation. The hydrogenated product of the oligomer or co-oligomer, that is, the hydrocarbon containing the bicycloheptane or octane skeleton may be used alone as a traction drive fluid, or may be used with another traction drive fluid as needed. They can be used in combination. In this case, the content of the dimerized hydrogenated product is not particularly limited, and may be appropriately selected depending on the type of the oligomerized hydrogenated product, the type of another traction drive fluid to be mixed, and the like. Preferably contains at least 5% by weight, preferably 30% by weight or more of oligomerized hydrogenated product of the entire traction fluid.

The other traction drive fluids to be mixed with the traction drive fluid from the oligomer obtained by the present invention include those conventionally used as traction drive fluids, as well as low traction performance when used alone. Various oils such as unoiled oil can be mentioned. For example, mineral substances such as paraffin-based mineral oil, naphthenic-based mineral oil, and intermediate-based mineral oil, alkylbenzene, polybutene, poly-α-olefin, synthetic naphthene, ester, ether and the like can be used in a wide range of liquid substances. 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. Has a structure in which two or more norbornane rings are directly bonded, an alkane derivative having two or more norbornane rings, and a compound having a structure in which two or more norbornane rings 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;
1,3-bis (bicyclo [2.2.1] heptyl) butane and the like can be mentioned.

Further, the traction drive fluid from the oligomer obtained by the present invention contains, as an essential component, a hydrogenated hydrocarbon of bicycloheptane or an octane skeleton, and optionally contains another liquid (such as a traction drive). Fluid, etc.), but if necessary, antioxidants, rust inhibitors, detergents / dispersants, pour point depressants, viscosity index improvers, extreme pressure agents, anti-wear additives, fatigue Various additives such as an inhibitor, an antifoaming agent, an oiliness improver, and a coloring agent can be used in an appropriate amount.

[0016]

Next, the present invention will be described with reference to Examples and Comparative Examples.
This will be described in more detail. Comparative Example 1 561 g (8 mol) of crotonaldehyde and 352 g (2.6 mol) of dicyclopentadiene were charged into a 2-liter stainless steel autoclave and reacted at 170 ° C. for 3 hours. After cooling the reaction solution to room temperature, Raney Nickel [M-300, manufactured by Kawaken Fine Chemical Co., Ltd.]
T] 18 g, hydrogen pressure 9 kg / cm ² , reaction temperature 1
Hydrogenation was performed at 50 ° C. for 4 hours. After cooling, the catalyst was filtered off, and the filtrate was distilled under reduced pressure to obtain 565 g of a 105 ° C./20 mmHg fraction. The fraction was analyzed by mass spectrum and nuclear magnetic resonance spectrum, and as a result, it was confirmed that the fraction was 2-hydroxymethyl-3-methylbicyclo [2.2.1] heptane. Next, 20 g of [gamma] -alumina (N612N, manufactured by Nikki Chemical Co., Ltd.) was placed in a flow-type atmospheric pressure reaction tube made of quartz glass having an outer diameter of 20 mm and a length of 500 mm. .5
A dehydration reaction is carried out at hr ^-1 to give 2-methylene-3-methylbicyclo [2.2.1] heptane and 2,3-dimethylbicyclo [2.2.1] hept-2-ene.
Hydroxymethyl-3-methylbicyclo [2.2.1]
490 g of a heptane dehydration reaction product was obtained. 460 g of the dehydration reaction product and 23 g of activated clay (Galeonite # 136, manufactured by Mizusawa Chemical Co., Ltd.) were placed in a 1-liter three-necked flask, and stirred at 140 ° C. for 3 hours to perform an oligomerization reaction. Table 1 shows the results of the reaction.

Comparative Example 2 The procedure of Comparative Example 1 was repeated, except that the dehydration reaction was carried out at 320 ° C. Table 1 shows the results of the reaction.

Example 1 In Comparative Example 1, the dehydration reaction was carried out at a reaction temperature of 300 ° C. and WH
The same operation as in Comparative Example 1 was performed, except that the operation was performed at SV of 1.0 hr ^-1 . Table 1 shows the results of the reaction.

Example 2 The same operation as in Comparative Example 1 was carried out except that the dehydration reaction was carried out at a reaction temperature of 290 ° C. Table 1 shows the results of the reaction.

Example 3 The procedure of Comparative Example 1 was repeated, except that the dehydration reaction was carried out at a reaction temperature of 300 ° C. Table 1 shows the results of the reaction.

Example 4 The same operation as in Comparative Example 1 was carried out except that the dehydration reaction was carried out at a reaction temperature of 315 ° C. Table 1 shows the results of the reaction.

Example 5 In Comparative Example 1, the dehydration reaction was carried out at a reaction temperature of 315 ° C. and WH
The same operation as in Comparative Example 1 was performed, except that the operation was performed at SV 2.0 hr ^-1 . Table 1 shows the results of the reaction.

Example 6 The same operation as in Comparative Example 1 was carried out except that the dehydration reaction was carried out at a WHSV of 2.0 hr ^-1 . Table 1 shows the results of the reaction.

Comparative Example 3 In Comparative Example 1, the dehydration reaction was performed at a reaction temperature of 335 ° C. and WH
The same operation as in Comparative Example 1 was performed, except that the operation was performed at SV 2.0 hr ^-1 . Table 1 shows the results of the reaction.

Comparative Example 4 The procedure of Comparative Example 1 was repeated, except that 522 g of allyl alcohol and 396 g of dicyclopentadiene were used instead of 561 g of crotonaldehyde, and 420 g of 2-hydroxymethylbicyclo [2 .2.
1] Heptane was obtained. This was subjected to a dehydration reaction and an oligomerization reaction in the same manner as in Comparative Example 1. The reaction result is
It is shown in the table.

Example 7 The same operation as in Comparative Example 4 was carried out except that the dehydration reaction was carried out at a reaction temperature of 290 ° C. Table 1 shows the results of the reaction.

Comparative Example 5 In Comparative Example 1, instead of 561 g of crotonaldehyde, 362 g of acrolein and dicyclopentadiene 3
400 g of 1,3-cyclohexadiene instead of 96 g
515 g of 2-hydroxymethylbicyclo [2.2.1] octane was obtained in the same manner as in Comparative Example 1 except for using. This was operated in the same manner as in Comparative Example 1. Table 1 shows the results of the reaction.

Example 8 The procedure of Comparative Example 5 was repeated, except that the dehydration reaction was carried out at 290 ° C. Table 1 shows the results of the reaction.

[0029]

[Table 1]

Comparative Example 6 An olefin (dehydration reaction product) obtained in the same manner as in Comparative Example 1 was treated with phosphotungstic acid (produced by Nippon Inorganic Chemical Co., Ltd.) on silica gel (produced by Fuji Devison Co., Ltd.).
CA-10], a flow-type atmospheric pressure reaction tube made of quartz glass having a diameter of 20 mm and a length of 500 mm and containing 5 g of a catalyst supported at 20% by weight was used.
SV) The oligomerization reaction was performed at 0.80 hr ^-1 . Table 2 shows the results of the reaction.

Example 9 An olefin (dehydration reaction product) obtained in the same manner as in Example 2 was treated with phosphotungstic acid (produced by Nippon Inorganic Chemical Co., Ltd.) on silica gel (produced by Fuji Devison Co., Ltd.).
CA-10], a flow-type atmospheric pressure reaction tube made of quartz glass having a diameter of 20 mm and a length of 500 mm and containing 5 g of a catalyst supported at 20% by weight was used.
SV) The oligomerization reaction was performed at 0.80 hr ^-1 . Table 2 shows the results of the reaction.

Comparative Example 7 In Comparative Example 6, activated clay was used instead of the catalyst in which phosphotungstic acid was supported on silica gel [manufactured by Mizusawa Chemical Co., Ltd.
Comparative Example 6 except that 5 g of galeonite # 136] was used.
An oligomerization reaction was carried out in the same manner as described above. Table 2 shows the results of the reaction.

Example 10 In Example 9, activated clay was used instead of the catalyst having phosphotungstic acid supported on silica gel [manufactured by Mizusawa Chemical Co., Ltd.
Example 9 except that 5 g of galeonite # 136] was used.
An oligomerization reaction was carried out in the same manner as described above. Table 2 shows the results of the reaction.

Comparative Example 8 Comparative Example 6 was repeated except that 5 g of silica alumina [N632L, manufactured by JGC Chemicals, Inc.] was used instead of the catalyst in which phosphotungstic acid was supported on silica gel.
An oligomerization reaction was carried out in the same manner as described above. Table 2 shows the results of the reaction.

Example 11 The procedure of Example 9 was repeated, except that 5 g of silica alumina [N632L, manufactured by Nikki Chemical Co., Ltd.] was used in place of the catalyst having phosphotungstic acid supported on silica gel.
An oligomerization reaction was carried out in the same manner as described above. Table 2 shows the results of the reaction.

[0036]

[Table 2]

[0037]

As described above, according to the present invention, the traction drive is carried out from a raw material containing an unsaturated bicyclo [2.2.1] heptane derivative and / or an unsaturated bicyclo [2.2.2] octane derivative. An oligomer which can be used as a working fluid can be obtained in a very high yield. Therefore, the oligomer obtained by the present invention can be widely used as a raw material of a fluid for traction drive used in various equipment products such as a continuously variable transmission for automobiles or industries, and hydraulic equipment.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI // C07B 61/00 300 C07B 61/00 300 C10M 105/04 C10M 105/04 C10N 30:02 30:08 40:04 70: 00 (58) Field surveyed (Int.Cl. ⁶ , DB name) C07C 13/42 C07C 2/08 C07C 13/40 C07C 13/44

Claims (1)

(57) [Claims] (1) 2-methylenebicyclo [2,2,1]
Butane, bicyclo [2,2,1] hept-2-ene, 2
-Methylenebicyclo [2,2,2] octane and bicyclo
B [2,2,2] oct-2-ene (however,
The compound is at least one selected from a methyl group and an ethyl group.
Which may have one substituent)
Is an oligomer that oligomerizes raw materials containing two or more
Wherein the compounds correspond to each other.
Alcohol at a temperature of 290-350 ° C.
Are those manufactured by Rukoto, and diene content in the raw material preparation of the oligomer is less than 1 wt%.