JPS6144118B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a power transmission fluid used in a power transmission mechanical device whose purpose is to hydraulically transmit power. More specifically, the present invention relates to a method for producing a power transmission fluid obtained by hydrogenating a specific fraction of pot residual oil produced as a by-product in the production of alkylbenzene, which is a raw material for cleaning agents. Traditionally, automotive transmissions, traction drives, hydraulics, shock absorbers, hydraulic steering, clutches, and other fluid-operated devices have been equipped with various techniques to reduce the friction and heat generated during their operation. lubricants are used. However, as various mechanisms have been developed for power transmission devices such as automatic transmissions in automobiles, and as large amounts of power and high speeds are required to be transmitted, fluids with performance suitable for the operation of these mechanisms are required. I started to do that. To operate these complex mechanisms, fluids must perform several different actions. The roles played by fluids include the removal of heat generated by the friction of the operating members of power transmission machinery and the lubricating action to reduce friction, but these are not the only roles fluids play. Other important roles also need to be played. A power transmission mechanical device that transmits power by means of a fluid essentially exerts its action through rolling friction contact between an input member and an output member through point contact and/or line contact. At the rolling contact surface, the fluid is trapped between the actuating members and forms a thin oil film, and at the same time very high pressure is applied to the oil film, causing the oil film to lose its fluidity and create rolling friction. Since power transmission by fluid is achieved by this rolling friction force, it is important that the fluid has a large rolling friction (expressed by a rolling friction coefficient) at the contact surface. Conventionally, power transmission fluids have been disclosed in U.S. Patent No. 3411369, U.S. Pat. -2229, etc., and it is proposed to use decalin, perhydroanthracene, polycyclohexyl, bicyclohexyl, dicyclohexyl, α-methylstyrene dimer hydride, adamantane, etc. as the fluid. has been done. However, the fluids proposed in the above materials have not been put into practical use due to reasons such as the rolling friction coefficient not being suitable for practical use and the difficulty in obtaining raw materials for implementation on an industrial scale. There aren't many. In JP-A No. 47-7664, α
-2,4 dicyclohexyl-2-methylpentane, a hydride of a linear dimer of methylstyrene, has been proposed. In order to industrially produce this power transmission fluid, a method is known in which α-methylstyrene is linearly dimerized and hydrogenated, but the raw material α-methylstyrene is expensive, Since side reactions such as cyclic dimerization and multimerization occur in the quantification step, various improvements remain to be made in order to carry out only the desired reaction. However, even if improvements are made in manufacturing technology, the use of expensive starting materials still leaves economic disadvantages unavoidable. Furthermore, low viscosity is an important element that the fluid should have. As seen in the development of automobile-related technology, in addition to the increase in horsepower, the amount of power transmitted has increased, and the operation of power transmission machinery has become faster, exposing operating members and power transmission fluid to harsh conditions. It will be. Therefore, since the power transmission fluid is used under severe conditions, the viscosity of the fluid becomes an important factor. In order to maintain high-temperature viscosity under conditions where the temperature rises due to high-speed operation, the above-mentioned disclosed technology proposes the addition of a viscosity index improver, high molecular weight polybutylene, etc., but the added substances has a small rolling friction coefficient and is not suitable for the original purpose of a power transmission fluid. That is, although it meets the purpose of maintaining high-temperature viscosity, it is inevitable that the original purpose of utilizing rolling friction will be sacrificed. As for specific indicators of the viscosity required for ordinary automobile transmission fluids, the fluid standard of "Dexron" by General Motors Corporation can be mentioned. Here 210〓
A high-temperature viscosity of 7.0 cSt is required as the minimum viscosity at (99℃). The inventors of the present invention have conducted extensive research on a method for manufacturing power transmission fluid that satisfies these various performance requirements and is economically inexpensive. The present invention was completed by discovering that a specific fraction of by-product oil during the production of alkylbenzene for cleaning agents is extremely suitable as a raw material for producing these power transmission fluids. That is, the present invention involves nuclear hydrogenation of a fraction mainly containing components with a boiling point (normal pressure equivalent) of 340°C to 365°C, which is produced as a by-product when producing alkylbenzene mainly containing an alkyl group having 10 to 15 carbon atoms. The present invention relates to a method of manufacturing a power transmission fluid manufactured by a method of manufacturing a power transmission fluid. The raw material for the method for producing the power transmission fluid of the present invention is a pot residue that is produced as a by-product during the production of alkylbenzene, which is produced in large quantities as a raw material for cleaning agents. Since no effective use had been established for this kettle residual oil, it was conventionally disposed of by incineration as fuel oil. Therefore, the fact that a synthetic oil with desirable properties as a power transmission fluid can be obtained by recovering a specific fraction and then subjecting it to hydrogenation treatment is an epoch-making and economical solution. It is clear that this is of great significance. As a method for industrially producing alkylbenzene for cleaning agent raw materials, branched olefins mainly containing _C10 to _C15 containing low polymers of lower olefins such as propylene tetramer, or _C10 to _C14 are mainly used. A linear olefin obtained by dehydrogenating a linear paraffin whose main component is a linear paraffin, or a linear α-olefin obtained by low polymerization of ethylene, and excess benzene are combined with a catalyst such as hydrogen fluoride or anhydrous aluminum chloride. Examples include the olefin method, in which alkylation is carried out in the presence of carbon dioxide, and the chlorine method, in which benzene is alkylated with a chlorinated paraffin mainly composed of _C10 to _C14 , using an anhydrous aluminum chloride catalyst. The reaction temperature in these production methods is preferably 0 to 80°C. The kettle residual oil, which is the raw material for the production method of the power transmission fluid of the present invention, can be suitably used by any of the above-mentioned methods. The bottom oil mainly contains monoalkylbenzenes, dialkylbenzenes, diphenyl compounds, substituted indenes, and substituted indanes, but by precision vacuum distillation, it can be distilled into a mixture of one- and two-ring aromatic hydrocarbons, i.e., heavy substances. alkylbenzenediphenyl compounds,
A heavy alkylate containing mainly substituted indenes and substituted indanes can be obtained. Although any method may be used for precision vacuum distillation of the pot residue, a batch vacuum distillation apparatus, a continuous vacuum distillation apparatus, etc. are preferably used. The heavy alkylate separated by distillation (a fraction mainly containing components with a boiling point of 340 to 365°C in terms of normal pressure) is
The composition varies slightly depending on the alkylation reaction conditions and the type of alkylating agent, but to give one example, the composition varies within the range shown in Table 1 below.

[Table] The power transmission fluid of the present invention is obtained by hydrogenating the above-mentioned heavy alkylate so that it is substantially free of aromatic components. Heavy alkylate has a boiling point range of 340 to 365℃ when converted to normal pressure.
Although it is preferable that the fraction contained in the In the above hydrogenation treatment, any commonly known aromatic ring hydrogenation catalyst can be preferably used. For example, nickel, nickel oxide, nickel diatomaceous earth, Raney nickel, nickel-copper, platinum, platinum oxide, platinum-activated carbon, platinum-rhodium,
Platinum-alumina, platinum-lithium-alumina, rhodium-activated carbon, palladium, cobalt, Raney cobalt, ruthenium, tungsten sulfide-nickel sulfide-alumina, etc. can be used favorably. The temperature of the hydrogenation reaction is 20℃ or higher and 250℃, and the pressure is from normal pressure.
It can be preferably carried out at a pressure up to 100 atmospheres. It is understood by those skilled in the art that the reaction conditions can be determined depending on the reaction format, for example, whether it is batchwise or continuous, the amount and pressure of hydrogen that can be used, and the time required for the reaction. is known in the art and is not an essential element of the method of the present invention.
In hydrogenation, it is important to reduce the remaining benzene nuclei to 2 mol% or less, and more preferably 0.5 mol% or less. Further, in the hydrogenation, an inert solvent such as a paraffinic solvent or a naphthenic solvent can also be used. Although it varies depending on the conditions of the hydrogenation process, if some light components may be generated due to decomposition etc. during normal hydrogenation process, vacuum distillation should be performed again to remove the light products. is sometimes desirable. Further, as the power transmission fluid, a fraction having a boiling point of 340 to 365° C. in terms of normal pressure is preferable, but a fraction having this fraction as a main component may also be used. Here, the power transmission fluid obtained by the present invention (hereinafter referred to as "the fluid of the present invention") will be compared with conventionally known power transmission fluids for further explanation. In order to demonstrate that the fluid of the present invention has excellent properties as a power transmission fluid, thermal stability and metal corrosion tests were conducted. In this test,
The acidity, viscosity change, and weight change of the metal test piece were measured for the fluid after it was heated for 120 hours at a temperature of 150° C. in an air constant temperature bath and deteriorated. The results shown in Tables 2 to 4 below were conducted under the following conditions. Sample amount: 300ml Container: Glass cylindrical container with inner diameter of 70mm Metal test piece: Iron, copper, tin, zinc, silver Test piece dimensions are 20mm x 30mm x
The surface area is the same at 1.5 mm.The comparative fluid is 2,4-dicyclohexyl-2-methylpentane (hereinafter referred to as "DHMP"), which is a hydride of a linear dimer of α-methylstyrene.
) and DHMP with 2wt% polyisobutylene dissolved as a viscosity increaser (hereinafter referred to as "DHMP
-PB) was used.

【table】

【table】

[Table] From the results in Tables 2 to 4 above, it is clear that the power transmission fluid of the present invention is an excellent fluid. In particular, according to the results in Table 4, viscosity improvers were added to improve the viscosity of conventional DHMP.
DHMP-PB has a negative effect on metals, especially iron and copper. The large weight loss of the copper test piece in the case of DHMP-PB is thought to be due to the large total acid value in Table 2. On the other hand, the inventive fluid and DHMP to which no viscosity improver was added had little effect on the metal test piece. Since power transmission fluids operate over a wide temperature range, viscosity is an important factor. This means that in addition to first satisfying a certain viscosity condition,
It is important that the viscosity changes during use as little as possible. From the results in Table 3, it is clear that the viscosity improver was added.
The viscosity change of DHMP-PB is large, and the result shows that the viscosity decreases. This indicates that the added polyisobutylene has worse thermal stability and decomposes due to long-term heating, indicating that the purpose of maintaining high-temperature viscosity cannot be achieved simply by adding a viscosity improver. It is. The above-mentioned "Dexron" fluid standard is one of the viscosity conditions that the power transmission fluid must first meet. According to the standard, the value is 7.0cSt or more at 210〓 (99℃). Table 5 below shows the viscosity measurement results for the inventive fluid and two comparative fluids.

[Table] As shown by the above results, the fluid of the present invention is an excellent fluid that maintains a desirable high temperature viscosity without adding a viscosity improver. Furthermore, as shown in Table 6, the rolling friction coefficient, which is the most important factor in power transmission, was determined by the fluid of the present invention.
It shows high values equivalent to DHMP. Measurement of rolling friction coefficient is carried out in "Lubrication", vol. 16, p. 573 (1971).
This was carried out according to the method described in .

[Table] As described above, the fluid of the present invention is epoch-making because it itself has a high high temperature viscosity and can be produced without using expensive raw materials such as α-methylstyrene. As explained above, the fluid of the present invention is an excellent power transmission fluid in itself, but when used in actual power transmission machinery, depending on the type of device and the conditions under which it is used, it may differ from the normal fluid. It goes without saying that, as in the case of lubricating oil, various additives can be added to improve the properties to suit the conditions of use. These additives include load-bearing additives, oil-based agents, anti-wear agents, extreme pressure additives, metal surface deactivators,
Rust inhibitors, corrosion inhibitors, cleaning dispersants, pour point depressants, antifoam agents, antioxidants, viscosity index improvers, lubricity agents, colorants, mold inhibitors, emulsifiers, demulsifiers, stain inhibitors etc., and these may be added as necessary. The method for manufacturing the fluid used in the above comparative test will be explained below. Production Example 1 Production of the fluid of the present invention (a) Distillation of heavy alkylate Straight chain olefin obtained by dehydrogenating _C10 to _C13 n-paraffin and benzene were distilled in the presence of a hydrogen fluoride catalyst for 30 min. From 500 g of residual oil in the pot when alkylbenzene, a raw material for cleaning agent, was obtained by reacting at ℃, the distillation temperature was 165
325 g of a fraction (heavy alkylate) at ~195°C (normal pressure equivalent: 335-375°C) was collected. The properties of this fraction are: specific gravity 0.870, viscosity 87cSt, initial distillation temperature 330℃,
It is a pale yellow liquid with a 5% point of 343°C, a 50% point of 355°C, a 95% point of 365°C, and an end point of 380°C. (b) Hydrogenation treatment 220 g of heavy alkylate obtained in (a) and 18 g of Raney nickel were placed in an autoclave with a capacity of 1, and combined with a hydrogen cylinder through a pressure control valve to maintain the pressure inside the autoclave at 35 atm. I made it hang down. Heating was started while stirring, heated at 100°C for 3 hours, at 160°C for 4 hours, and finally at 180°C for 3 hours to complete the hydrogenation. After cooling, the mixture was passed through a Raney nickel catalyst to obtain 230 g of hydrogenated heavy oil. In order to remove the decomposition products generated during the hydrogenation process, this was recirculated to 3 mm.
Distillation was carried out under reduced pressure of Hg to obtain 226 g of fraction with a distillation temperature of 155-200°C. This is the fluid of the present invention.
The fluid of the present invention has a specific gravity of 0.886 (15/4℃) and a viscosity of
91.2cSt〔100〓(38℃)〕, 8.44cSt〔210〓(99
)], it is a colorless liquid with a flash point of 198°C. Additionally, as a result of ultraviolet absorption analysis, residual benzene nuclei were found to be 0.27
It was in mol%. (c) Type analysis of the fluid of the present invention The fluid of the present invention is a mixture of multiple components. Table 7 shows the results of type analysis by mass spectrometry.

[Table] The composition numbers indicate the relative intensities of the peaks determined by mass spectrometry. Production Example 2 Production of 2,4-dicyclohexyl-2-methylpentane (DHMP) (a) Linear dimerization of α-methylstyrene 500 g of α-methylstyrene with a purity of 99%, 25 g of mesityl oxide, and acid clay (Mizusawa Chemical) (KK)
5 g of Galeonite 036) was placed in a glass reactor equipped with a stirrer, and heated while stirring.
An exothermic reaction started at a temperature of around 65°C, and heating was stopped. When the temperature rose to 100°C, it was cooled and reacted at 100°C for 20 minutes. When the heat generation decreased, it was heated again and the reaction was continued at a temperature of 95 to 100°C for an additional 3 hours. After the reaction, the acid clay was separated and distilled under reduced pressure at 10 mmHg to obtain 50 g of light fraction (including mesityl oxide and unreacted α-methylstyrene) and 415 g of dimer (distillation temperature: 170-180℃). ) was obtained. According to glass chromatography analysis, the purity of this linear dimer is 98%, with the remaining 2% being
was a cyclic dimer. (b) Hydrogenation reaction 400 g of the mixture of 98% α-methylstyrene linear dimer and 2% cyclic dimer obtained in item (a) above and 43 g of Raney nickel were charged into autoclave 1 and hydrogenated. . The operation was carried out in the same manner as in section (c) of Production Example 1. In order to remove the decomposed products produced in the hydrogenation step, distillation was carried out again under reduced pressure of 3 mmHg to obtain 409 g of a fraction with a distillation temperature of 145 to 160°C. This was the DHMP used in the comparative experiment. DHMP is specific gravity
0.884, viscosity 22.4cSt [100〓(38℃)], 3.62cSt
It is a colorless fluid with a temperature of [210〓(99℃)]. Further, as a result of ultraviolet absorption analysis, residual benzene nuclei were found to be 0.27 mol%. In other words, the DHMP used to explain the present invention is 2
% cyclic dimer hydride and 98% linear dimer hydride.

Claims (1)

[Claims] 1 C ₁₀ to C ₁₅ alkyl group is formed by alkylating a C ₁₀ to C ₁₅ branched olefin, linear olefin, linear α-olefin and/or chlorinated paraffin with benzene. The boiling point range is a by-product when producing alkylbenzene, which mainly contains
A power source characterized by hydrogenating a by-product oil fraction, which is a mixture of one- to two-ring aromatic hydrocarbons, at a temperature of 340 to 365°C (converted to normal pressure) so that it substantially no longer contains aromatic components. Method of manufacturing transmission fluid. 2. The method for producing a power transmission fluid according to claim 1, wherein the alkylbenzene is an alkylbenzene for cleaning agent raw material. 3 The hydrogenation treatment is carried out in the presence of an aromatic ring hydrogenation catalyst at a reaction temperature of 20°C to 250°C and a reaction pressure of normal pressure to 100 atm, so that the residual benzene nuclei after the hydrogenation treatment is 2 mol% or less. A method for producing a power transmission fluid according to claim 1 or 2, characterized in that the method is carried out in such a manner that: