JPH0253893A - Phosphoric ester lubricant - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the use of certain phosphate ester compounds as lubricants, particularly in traction drive devices. II Concerning its use as a lubricant.

Lubricants are used in various fields of mechanical engineering and are of particular importance in static friction drives. In a broad sense, static friction is defined as the adhesive friction of an object on a surface on which the object moves along its -L. A static friction drive is a device that transmits torque from an input element to an output element through a few contact points or lines of contact, typically in C1 rolling motion, by static friction between the contact elements. Although the friction elements are said to be in contact, it is generally accepted that a fluid film exists between the static friction elements. This eliminates the need for fluid to lubricate the bearings and other moving parts associated with the drive, preventing wear on the contact surfaces.Thus, instead of metal-to-metal rolling contact, There is a film of fluid introduced into the contact area and interposed between the metal elements. The nature of this fluid largely determines the capacity and performance of the static friction drive. Most static friction drives are approximately The coefficient of static friction is approximately 4.
It is designed to operate using static friction fluids that preferably have a viscosity of ~20,000 mPa, s, and good temperature and oxidative stability. The fluid should also not corrode common construction materials and have good fire resistance properties and low wear rate properties.

Mineral-based oils are rather unsatisfactory lubricants for boat fishing as their coefficient of static friction (wear) is low and therefore the maximum tangential force that can be transmitted by the friction wheel at a given load applied to the gear is low.

It has been discovered that certain organophosphate esters constitute good lubricants and stiction fluids. Accordingly, the present invention provides the use of organophosphate esters having the general formula (1) as lubricants and in particular as static friction fluids.

C! optionally substituted with one or more Al1 groups! i-7 represents a cycloalkyl group, and [< represents 1 (or an alkyl or aryl group). Preferably it contains from 1 to 6 carbon atoms, and groups with up to 4 carbon atoms are particularly suitable in terms of physical properties +1 and material F31 cost. Preferred when R2 is aryl or aryl. The group is C1-6 alkyl, more preferably C4-6
A branched alkyl group (eg, neopentyl), or a phenyl group, optionally with one or more alkyl substituents (eg, methylphenyl).

A preferred organophosphorus l1i-L stellate having the formula ■ is R
This is a compound in which 1 represents an optionally alkyl-substituted Schiff 111/\xyl group. Advantageously, R1 is cyclohexyl or methylcyclohexyl and R2 is cyclohexyl, methylcyclohexyl, methylcyclohexyl or C4-
It is a 6-branched alkyl group.

Particularly preferred esters with 2 J- are R1 and 1 (
2 is selected from a 2-methylcyclohexyl group and a 3-methylcyclo[1-hexyl group, respectively.

Organophosphate esters are well known compounds and can therefore be prepared by well known procedures such as reacting phosphoryl chloride with a suitable alcohol in the presence of a base such as pyridine or triethylamine and optionally also a solvent. . Of course, optimal reaction conditions will vary depending on the alcohol used. After the reaction of cyclohequinanol and phosphoryl chloride, 25%
It has been found that good results are obtained if the reaction is carried out at temperatures not exceeding 0.degree. C. and the product is purified by crystallization using diebruedel. In the case of the methylcyclohexyl analog, it is reacted under similar reaction conditions and purified using a thin film evaporator.

The viscosity properties of the ester compounds described above are, for example, always suitable for use in friction wheel gears, where the ester compounds are used in admixture with conventional grease thickeners. The above-mentioned thickeners are IJ additives commonly used to thicken the viscosity of mineral oils to lubricating viscosity, and include metal resins, synthetic polymers, organosi] Kirin, clay, pen 1 ~ night and -' 1 ] Includes organic and inorganic materials such as id-like silica. The viscosity properties of the compound used in the static +1 friction drive are suitable such that the compound can operate at temperatures between 130°C and 150°C. For this purpose, the ester compound in the lubricant according to the invention has a viscosity of at most 1000, preferably 2507/S at 40° C.
It is advantageous to have a viscosity at 0° C. of at least 1, preferably 3 mj/s.

The compounds of the invention can be used as lubricants in various mechanical engineering fields. The above ester compounds exhibit excellent lubrication performance in static friction drive devices1
The invention therefore particularly provides the use of these ester compounds as static friction fluids and the operation of static friction drives in which such Nisdel constitutes the static friction fluid.

Use of the ester compound of the present invention as a lubricant itself
It is possible to It may also be mixed with other lubricants such as mineral or synthetic oils, and various additives such as VI improvers, pour point depressants, dispersants, detergents, anti-corrosion agents, etc. It may be added to this compound. Particularly advantageous blends in the field of stiction fluids are blends with polyolefins, especially poly-alpha-olefins, especially polyisozotylenes, since the presence of the polymer can effectively increase the coefficient of stiction of the fluid blend. The molecular group of the polyolefin blend component is 500 to 100.
One example of a suitable polyisobutylene is III/VI3, where the proportion of polyolefin is 0 to 70% by weight.

The following examples describe the preparation of representative compounds used in the present invention, along with their frictional properties and other physical properties.

: 1 shiku [1 to 1 silhosno 3-- shijikuro 1]
In methane (3,! jj!
95.0g.

7.5 m) was stirred in a dry nitrogen atmosphere 1.
Phosphoryl chloride (382.5u, 2.sm>) was added in portions over a period of 1-2 hours, maintaining the temperature of the reaction mixture between 15.-25.degree. C. during the addition.

After the addition was complete, stirring was continued at ambient temperature for an additional 18 hours, after which the mixture was filtered. The organic solution was washed with water (3×51), dried (over 1304) and the solvent was evaporated in vacuo at 30° C. to give a pale yellow viscous oil (730.3 g).

When this was left to stand, it solidified slowly. This crude oil was dissolved with stirring in a dichloromethane (750 μm) and stirred in a dry ice/alloy cooling bath.
0~--;] Cooled to 0°C. Filter the precipitate, 25
Drying in vacuo at <RTIgt;C</RTI> afforded tri(Schif[1hexyl)phosnoe-1-(520,09') as an ono-white solid with a melting point of 48-50<0>C.

■Methylcyclohexanol (T grade, contains isomer mixture: 2.08Kg in nitri(methylcyclohexyl)phosphate dichloromethane (10)
18.2m) and pyridine (1,44KL 18.2
The solution containing TliL) was stirred under a dry nitrogen atmosphere and phosphoryl chloride (930.2 g, 6.077 n) was added while maintaining the temperature of the stirred reaction mixture between 1:8 and 25 °C. It was added in portions over a period of 5 hours. After the addition was complete, stirring was continued at ambient temperature for an additional 18 hours, after which the resulting mixture was filtered and mixed with water (4 x 6ρ).
Washed with and dried (HgS04-1), the solvent was
After evaporation in vacuo at 0° C., the crude external acid was obtained as a viscous oil. After leaving the crude oil to dry overnight, it was filtered, and unreacted methyl Schiff [Giant: 1 linole and other volatile impurities were removed by KDl, -4Ab (85°C and 0.8 mm 1 L + (107 Pa)). Evaporation in C) gave the product as a clear viscous oil (1.75 Kg) containing a mixture of different isomers.

14 cups l2X Example ■ was repeated. However, 2-methylcyclohegizanol, 3-methylcyclohedizanol, 3-methylsif[1 to 1 to 1 → nanol] and 4-methylsif to 1 to 1 to 1 sanol (in each case, cis- and trans- In one example, tri(2-methylcyclohexyl) phosphate (oil)
.

In Example IV, 1 edge-(3 iJ<sulfate (oil).

In Example ■, the bird Phosphate (oil) was prepared.

(4-Methylcyclo↓sil) Methylcyclohexyl) Phosphoryl chloride (1
15, OLJ, 0.75m) and cresol (T grade.

A solution containing the mixture of isomers) (81.1 g, 0.75 TrL) was stirred in a dry nitrogen atmosphere at 1-5°C. Pyridine (59,3y, 0.75yn, ) was added in portions over 20-30 minutes, maintaining the wetness of the reaction mixture below 20°C during the addition.

Cool to ~15°C and transfer to Methylschiff IJ 1 linole (same industrial grade as Example ■) (205,!ig, 1.
8 m), and the temperature of the reaction mixture during addition was 15-20 m.
The mixture was added over a period of 30 minutes while being kept at 40°C. −・
After continued stirring overnight, the mixture was diluted with water (4x
500 me), dried (over magnesium sulfate) and the solvent was evaporated in vacuo. The resulting crude oil (31!1jJ) was subjected to a thin film evaporator (150 °C and 0.8 mrn HCIHE) to remove volatile fl impurities.
force (at 107 Pa)), it is obtained as a brown oil containing bicarbonate.

A solution containing phosphoryl chloride (76,77,0,!im) in dichloromethane (500 mi!'I) was stirred at 1!i °C under an atmosphere of dry nitrogen, and then dissolved in phosphoryl chloride (76,77,0,!im) in dichloromethane (500 mi! , G,5TI
L) was added over a period of 15 minutes while maintaining the humidity of the reaction mixture below 20°C during stirring. After stirring this mixture for 24 hours, 10...1! Pyridine (130,5 g, 1.6
57IL) was added little by little. After this, methylschiffhexynol (same industrial grade as Example ■) (137,
1 SO, 1.2 TL) was added while maintaining the temperature of the stirred mixture between 10 and 20°C during the addition. Then 1
After stirring for 18 hours at 5-20°C, the solution was washed with water (4 x 500 m), dried (over magnesium sulfate) and the solvent was evaporated in vacuo to give the crude product ( 200.3 g) was obtained as a yellow oil.The crude oil was evaporated to M 119 (150 °C and 0.7 mm
When purified by evaporation at g pressure (at 93 Pa), bis(medylcyl-1/\xyl)° sinoneobentylphosphonoate (131,09) is a sticky bamboo containing a mixture of different isomers. Obtained as a yellow oil.

b Example ■: lt Friction Coefficient Measurements - Fj Friction Measurements All measurements were carried out on a two disc machine. Hardened copper discs are fixed to the ends of the two shafts in tangential contact with the base. It is also possible to press the disks together with a load of 0.-2ooKgr.Secondly, it is also possible to use a radial force. Each disk is driven by an electric motor. The rotational speeds of the two discs differ only once there is slippage.

A measuring device is used to measure the transmitted friction torque between the electric motor and the shaft holding the test specimen on the 1 side. Equilibrium position (
Vertical balanced position
n) with a pendulum swung out of the I-cog gear power R1
, and the sine of the inclination angle is in the range of 1 to Luk. The amount of torque depends on the design and dimensions of this equipment.]
Can be precalibrated in advance. The coefficient of friction is divided by the product of the radius internal force multiplied by the lower disk radius. ' determined by the measured torque.

Both discs used had a diameter of 50.0 m, the upper disc had a width of 3 m and the lower disc had a width of 10 m. The maximum axial speed was eoerpm and the average tangential (surface) speed was 1.48 m5''. The slip used was 9.1%.

All experiments were performed at ambient temperature (21°C ± 2°C).

1l of 0.69.0.97.1.19.1.38GPa
Measured at a load corresponding to the Ertzian stress.

The friction coefficients of the above compounds are shown in the table below. Melting point is 48-50
For the compound of Example ■ where the temperature is
Measured in supercooled liquid at (±2)°C.

The kinematic viscosity properties of the compounds are also shown in the following table.

The friction coefficients of the compounds are all good, but in Examples
Note that the coefficient of friction of the compound is surprisingly high.

Output A injection λ n'shi ° Inoternashitanal 1 research.

Mart Harahei Pei-way

Claims (10)

[Claims] (1) General formula I ▲There are mathematical formulas, chemical formulas, tables, etc.▼ I (In the formula, each group R^1 represents a saturated alicyclic group optionally substituted with one or more alkyl groups, and R^ 2 is R^
1 or representing an alkyl or aryl group) as a lubricant. (2) The use according to claim 1, wherein the alkyl group present in the ester contains 1 to 6 carbon atoms. (3) The use according to claim 1 or 2, wherein R^1 represents an optionally alkyl-substituted cyclohexyl group. (4) The use according to claim 3, wherein R^2 represents an alkyl group having 1 to 6 carbon atoms, an optionally alkyl-substituted phenyl group, or an optionally alkyl-substituted cyclohexyl group. (5) Use according to any one of claims 1 to 4, wherein the ester compound has a kinematic viscosity of at most 1000 mm^2/s at 40C and at least 1 mm^2/s at 100C. (6) The use according to any one of claims 1 to 5, wherein R^1 is cyclohexyl or methylcyclohexyl and R^2 is cyclohexyl, methylcyclohexyl, methylphenyl or a C_4_-_6 branched alkyl group. . (7) R^1 and R^2 are each selected from 2-methylcyclohexyl group and 3-methylcyclohexyl group,
Use according to claim 6. (8) A lubricant composition containing the organic phosphate according to any one of claims 1 to 7 as a main component. (9) Use of the organic phosphate ester according to any one of claims 1 to 7 or the composition according to claim 8 as a static friction fluid. (10) A method for operating a static friction drive device, wherein the static friction fluid is the organic phosphate ester according to any one of claims 1 to 7 or the composition according to claim 8.