JPS6143400B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to the production of paraffin base oils, in particular for use in hydraulic systems with mechanical transmissions, hydraulic shock absorbers, etc. For a liquid to be useful as a hydraulic fluid, it must have a fairly high boiling point, as low a freezing point as possible, a high viscosity index, and good lubricity. Since sealing joints in hydraulic transmission systems are typically made of elastomeric bodies, it is important that the fluid be virtually inert to the particular elastomeric body that comes into contact with the fluid. In particular, the fluid must not affect the mechanical properties of these materials and must not cause excessive swelling or contraction of the elastic body. Fluids based on glycols or glycol polyesters have been used in some cases, but these products are expensive and cumbersome in certain applications due to their hydrophilic nature. The use of natural and synthetic hydrocarbon oils is also known, but the hydrocarbon oils must have a low freezing point and a flash point in an open container of 100° C. or higher. Furthermore, the viscosity must be precisely matched to the particular application for which the fluid is intended. Since the viscosity range of typical hydrocarbon bases for hydraulic fluids ranges from 2 to 30 cSt at 37.8°C, it is difficult to produce oil suitable as a base for hydraulic fluids by refining crude oil fractions. Obtaining a mineral oil with sufficient inertness to elastic bodies and a sufficiently low freezing point requires very extensive refining and is expensive. It is also known that in some cases oils obtained by the polymerization of light olefins can be used as a basis for hydraulic fluids. The properties of these synthetic oils,
In particular, its oxidation resistance is further improved by hydrogenating the oil (RE Hatton, "Introduction to Hydraulic Fluids" 1962.P .181
~182]. Additionally, there are numerous patents relating to the production and use of this type of oil. For example, French Patent No. 794397 specifies 1935
For as many years ago, it was described that light olefins such as propylene and isopropylene could be polymerized and the resulting polymers hydrogenated to produce lubricating oils. In US Pat. No. 2,360,446 it is proposed to use compositions containing oils of the above type for the lubrication of internal engines. The oils considered in this specification have a viscosity of greater than 15.5 cSt at 99.9°C. According to this specification, this oil can be produced by polymerizing propylene or isobutylene in the presence of a Friedel-Crafts catalyst and then hydrogenating this polymer. However, the viscosity of these synthetic oils varies widely and fractional distillation must be carried out to obtain fractions with the desired flash point and viscosity, the yields of which are correspondingly low.
Moreover, these synthetic oils are composed of isoparaffinic hydrocarbons whose degree of branching and purity are variable, making it difficult to maintain a constant swelling effect on the elastomer. FR 1 357 634 proposes a base oil for hydraulic fluids which is particularly satisfactory with respect to its effect on elastic bodies. The process for producing this oil is related to the process for producing industrial tripropylene and tetrapropylene, which involves the oligomerization of propylene over a phosphoric acid-based catalyst at a temperature of at least 140°C. The oligomers are subjected to fractional distillation. According to French Patent No. 1357634, hydrogenation of these oligomers, i.e. oligomers whose initial boiling point is above 175°C or fractionated between 200 and 300°C, produces very high quality products. This results in an oil that is perfectly suitable as a base oil for hydraulic fluids. However, this process has the disadvantage that the propylene oligomers produced at a temperature of 140° C. and in contact with phosphoric acid contain only a small proportion of the desired fraction. While the demand for high quality hydraulic fluids is constantly increasing, the demand for tripropylene and tetrapropylene is not. The inventors have therefore devised a process for obtaining a suitable oil in high yield, which is independent of the production of tripropylene or tetrapropylene. The polymerization of propylene, isobutylene and n-butene is carried out regularly in the liquid phase at temperatures below 100 DEG C. and even at lower temperatures in the presence of Friedel-Crafts catalysts, as described for example in UK Patent No. 1148966. This patent specification also discloses that the average molecular weight of the polymer obtained depends, inter alia, on the reaction temperature and the activity of the catalyst. Other things being constant, the average molecular weight of the product will be higher as the reaction temperature is lowered. The present invention provides a process for producing a highly paraffinic base oil having a flash point above 100°C and a viscosity within the range of 2 to 30 cSt (37.8°C), which process comprises producing propylene in the liquid phase in a three-foot oligomerize at temperatures between 20°C and 80°C in the presence of a boron catalyst,
This is a method in which the catalyst and the oligomers produced are separated and the oligomers are hydrogenated as a fraction thereof. It is necessary to distill within the temperature range of 20 DEG C. to 80 DEG C., the reaction temperature selected to obtain oligomers which yield oils of the required viscosity during hydrogenation. Although the process of the invention distills the oligomers to separate the fraction with the desired viscosity and flash point even when the yield is high, the process of the invention nevertheless produces the desired oil in high yields. It can be manufactured with The present invention has discovered that when oligomerization is carried out within the temperature range and catalyst type specified above, hydrogenation produces oligomers having the required average molecular weight and viscosity to provide a base oil for hydraulic fluids. It is thus possible, if necessary, to obtain the desired oil in high yield by subsequent hydrogenation and fractional distillation. The most favorable oligomerization temperature for obtaining certain oils can be found experimentally within the temperature range specified above. The hydrogenation saturates the olefinic bonds present in the molecules of the oligomer and is continued until the bromine number of the product is substantially zero, and in some cases less than one. Any conventional hydrogenation method may be used, the conditions of the reaction, especially the temperature, being adjusted so that no appreciable decomposition occurs. Usually, if hydrogenation is carried out at temperatures below 220°C, virtually no low molecular weight products will be produced. A preferred method of the invention is to use catalysts based on nickel, nickel-molybdenum, nickel-tungsten, nickel-cobalt or oxides of one or more of these metals. Appropriate pressures and temperatures will vary depending on the activity of the catalyst used. For example, the hydrogenation can be carried out with a nickel-cobalt based catalyst at a temperature of 180 DEG to 220 DEG C. and a pressure of 10 to 100 bar. The oil obtained in this way is substantially pure, typically 99%
It is composed of the above isoparaffin hydrocarbons. Furthermore, the inventors have found that when the oil is produced from propylene, the oil has a particularly low swelling power for elastic bodies. A preferred method for oligomerizing propylene of the present invention is carried out as follows. A reactor with stirring and cooling means is used to maintain the reaction mixture at a predetermined temperature, and the pressure is such that the mixture is liquid.
Generally a pressure in the reactor of 30 bar is sufficient. In the reactor, propylene is contacted with 0.04-0.08% water and 0.5-0.8% anhydrous boron trifluoride.
These ratios are expressed by weight relative to the weight of propylene. The reaction temperature is generally between 20 and 80°C, and an average reaction time of 30 minutes is usually sufficient to completely react the propylene. The reaction products contain gaseous organisms, mainly boron trifluoride and propane, which is the main impurity of the propylene used as feedstock. These gaseous products are separated using any suitable conventional means well known to those skilled in the art. After degassing, the oligomer contains boron and fluorine compounds derived from boron trifluoride, which can be removed by washing the oligomer with an alkaline solution. This oligomer is then fractionally distilled if necessary;
The fraction with the required flash point and viscosity is separated and finally the oligomers are hydrogenated. The inventors have found that the oil produced has a less swelling effect on elastomers than hydrogenated polypropylene obtained by other methods. The oil produced from propylene by the method of the invention is very useful as a hydraulic fluid and has a small swelling effect on most elastomers, and some elastomers undergo slight contraction when in contact with this oil. . Generally, isoparaffin oil has a stronger swelling power as the content of cyclane (cycloparaffin), which is an impurity, is higher. Surprisingly, the inventors have found that pure isoparaffin causes significant shrinkage of certain elastomers, particularly polyurethane-based elastomers. This shrinkage is detrimental to the strength of the connections in the hydraulic circuit, but it can be overcome by mixing with certain polycyclane oils. Therefore, the present invention makes it possible to produce oil for hydraulic fluids having a predetermined swelling power, and further, by incorporating a small amount of naphthenic oil into the oil produced by the method of the present invention, and adjusting the amount of naphthenic oil. , can provide the final oil with the desired swelling power for the particular elastomer to be used with the oil. The naphthenic oil used in this composition is preferably a natural or synthetic oil whose molecules consist essentially of saturated hydrocarbons consisting of several fused cyclane. In the method of the present invention, any naphthenic oil that has a sufficiently high flash point and is substantially free of aromatic hydrocarbons can be used. Oils containing a high proportion of aromatic hydrocarbons influence the mechanical properties of the elastic body. The presence of isoparaffinic hydrocarbons in this oil does not cause any problems. The viscosity of the naphthenic oil is of little importance as long as the oil product containing it has the desired viscosity. Preferably, naphthenic oils are used whose viscosity is between 10 and 100 cSt at 37.8°C. It is possible to use naphthenic oils obtained from suitable crude oils by conventional distillation and refining operations. Nevertheless, it is very difficult in practice to obtain essentially aromatic carbon-free naphthenic oils from petroleum. For this reason it is preferred to use synthetic oils. Preference is given to using synthetic oils consisting of cycrane hydrocarbons whose molecules contain at least three fused rings, each ring having 5 carbon atoms. This kind of oil is 80~175℃
can be conveniently prepared from the steam-cracked naphtha fraction of Naphtha cuts of this type contain high proportions of cyclopentadiene, dicyclopentadiene and mono- or dimethyl derivatives of these cyclodienes. The cyclodienes present in this naphtha can be obtained, for example, by heating the naphtha at a temperature of about 260° C. and a pressure of 12 to 15 bar for 2 to 4 hours.
By keeping it for a long time, it can be condensed to polycyclopentadiene. The reaction product is then diluted with an inert solvent and then hydrogenated to obtain a naphthenic oil. Hydrogenation can be carried out in a conventional manner to saturate the ethylene bonds in the polycyclopentadiene molecule and produce the corresponding polycyclane hydrocarbon.
Finally, the hydrogenation mixture is fractionally distilled to recover the solvent and separate the fraction with the desired flash point and viscosity. By varying the proportion of naphthenic hydrocarbons contained in the oil obtained according to the invention, the swelling power of the final composition can be adjusted very precisely, and even higher amounts of naphthenic oil, up to 20%, can be used. The inventor has produced a product from propylene according to the present invention, and the weight of 3
It has been found that oils containing ~10%, more preferably 5-8% naphthenic oils of the above type exhibit an absolutely satisfactory behavior when in contact with conventional elastic bodies. This polycyclane hydrocarbon can be incorporated into the final oil by simple mixing. On the other hand, suitable fractions of oligomers obtained by the process of the invention can be mixed with suitable proportions of polycyclopentadiene and hydrogenated mixtures thereof. The invention also provides an oil obtainable by the method described above. Also provided are hydrocarbon-based hydraulic fluids containing a high proportion of such oils, which hydraulic fluids are constituted by a base oil and suitable additives. The oils of the present invention may also contain other conventional additives such as viscosity index improvers, extreme pressure additives, anti-wear agents and antioxidants. Although the invention is illustrated, the invention is not limited by these examples. Example 1 A base oil for hydraulic fluids having a viscosity of 16-18 cSt at 37.8°C was prepared as follows. Propylene was contacted with 0.05% by weight of water and 0.06% by weight of boron trifluoride in a stirred and cooled reactor at a pressure of 20 bar and a temperature of 30°C. this mixture
It was left in the reactor for 30 minutes. The reactor was removed and the mixture was expanded from 20 bar to 1 bar to evaporate the propane and boron trifluoride. The remaining liquid was washed with dilute soda solution to obtain an oligomer with the following properties. Distillation (according to standard ASTMD-86) Distillation volume (%) Temperature °C Initial boiling point 276 10 300 50 328 90 359 End point 361 Viscosity (37.8°C) 15 cSt Average molecular weight 340 Bromine number 44 This oligomer was distilled over a nickel and cobalt based catalyst to 18 Hydrogenation was carried out under a pressure of bar and a flow of hydrogen at a rate of 0.25 h ^-1 . The base oil for hydraulic fluids obtained by hydrogenation had the following properties. Viscosity (37.8℃) 16.56cSt Viscosity (99℃) 3.20cSt Viscosity index 42 Flash point, open container 144℃ (Cleveland) Density (15℃) 0.819 Freezing point -51℃ Bromine number 0.4 Aromatic content 0.3% by weight used The yield of the final product based on the weight of propylene was greater than 99%. Example 2 A base oil for hydraulic fluids having a viscosity of 4-6 cSt at 37.8°C was produced. For propylene oligomerization, the reactor temperature is 70℃.
The yield of oligomer based on the weight of propylene used was 99.5.
% or more, and the characteristics of the oligomer were as follows. Viscosity (37.8°C) 5.5 cSt Flash point in open vessel 95°C (Cleveland) Average molecular weight 265 This oligomer was fractionally distilled to separate a fraction with the desired viscosity and flash point. To do this, it was divided into three fractions. The first fraction (7% by volume), the main fraction (79% by volume) and the residual fraction (14% by volume). The above main fraction (79% by volume) had the required properties. Viscosity (37.8°C) 4.8 cSt Flash point in open container 110°C (Cleveland) Average molecular weight 260 This fraction was treated and hydrogenated as in Example 1 except that the temperature was 180°C. did. The obtained oil (A) had a yield of 79% (weight) based on the weight of the propylene used, and had the following characteristics. Viscosity (37.8℃) 4.9cSt Viscosity (99℃) 1.5cSt Density (15℃) 0.806 Freezing point -60℃ Cleveland flash point 110℃ Bromine number 0.2 Aromatic hydrocarbons 0.2% by weight Distillation (ASTM method D-86): Distillation Volume (%) Temperature (°C) Initial boiling point 237 10 249 50 278 90 314 End point 326 For comparison, the same type of oil was prepared using a method similar to that of French patent No. 1357634, i.e., propylene was mixed with phosphoric acid deposited on diatomaceous earth. It was produced by contacting at 190°C to oligomerize and separating the fractional fraction at 200-300°C. In this method, the yield was 5% by weight based on the weight of propylene used. Oil B obtained by hydrogenating this fraction differed from oil (A) in its cycloparaffin content and its behavior towards elastic bodies. The compositions of the two oils as measured by mass spectrometry are as follows.

[Table] Polyurethane rubber samples were immersed in each oil at 130°C for 20 days. As a result of this test,
The volume of the sample immersed in Oil A decreased by 6.9%, and the volume of the sample immersed in Oil B increased by 3.8%. Reference Example 1 Oil A revealed in Example 2 and naphthenic oil (C) were mixed to produce two types of oils having a certain swelling power. Oil C is a naphtha fraction obtained by steam cracking and distillation at 80 to 175°C, and contains approximately 60% of the dimer of cyclopentadiene and methylcyclopentadiene.
% of the above naphtha fraction was heated to 260° C. in an autoclave and then kept at this temperature for a further 2 hours. The contents of the autoclave were then reduced by distillation until a residue of 100 Kg was obtained. The residue was a resinous, very dark brown substance with a bromine number of 60. This was treated with 500 kg of a hydrocarbon solvent distilled at 150-180°C, and the resulting solution was heated with hydrogen over nickel-based and tungsten-based catalysts at 240°C and 60 bar until the bromine number of the product became zero. It became. The hydrogenation product was distilled to separate the solvent, 40 kg of oil (oil C) of the 280-380° C. fraction and 60 g of residue. Oil C was substantially colorless and had the following characteristics: Density (15°C) 1.019 Refractive index 1.529 Viscosity (37.8°C) 80.5cSt Viscosity (99°C) 7.2cSt Bromine number 1 or less Flash point (Cleveland) 142°C Freezing point -12°C Two mixtures were produced. One is 93% oil A and 7% oil C, the other is 86% oil A and 14
% of oil C. These proportions are by volume. A sample of polyurethane rubber was immersed in a mixture of Oil A and each of the above at 130°C for 20 days. The mechanical properties of each sample were measured before and after each highly demanding test, and the change in each property was calculated in relative expression (% of initial value). The following results were obtained.

[Table] Yule
Breaking load −85 −85 −83
Volume −6.90±0.5 +2.2±0.5 2.7±0.5
Embodiments of the invention are as follows. (1) The olefin is propylene, and the catalyst is 0.04 to 0.08% by weight of water and 0.5% to 0.8% by weight.
The manufacturing method according to claim 1, characterized in that the oligomerization is carried out in a temperature range of 20 to 80°C.

Claims (1)

[Claims] 1. Oligomerize propylene in a liquid phase in the presence of a boric acid trifluoride catalyst at a temperature of 20°C to 80°C, 2. Separate the catalyst and oligomer, and if necessary perform fractional distillation, and then, 3. Hydrogenating the oligomer or its fraction, characterized by a flash point of 100°C or higher, 37.8°C
A method for producing a paraffin base oil with a high yield and a viscosity within the range of 2 to 30 centistokes and an isoparaffin content of 99% or more.