JPH0373598B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention uses a polyether compound as an active ingredient,
This invention relates to a lubricating oil with excellent wastewater treatment properties. Polyether-based synthetic lubricating oils have excellent lubricity, low-temperature fluidity, stability, etc., and can be synthesized in a wide range of grades from water-soluble to oil-soluble, so they are suitable for hydraulic oils, metal processing oils, heat transfer oils, etc. It is widely used as a lubricant. However, polyether-based synthetic lubricating oils, especially water-soluble polyethers used as bases or solvents for water-based lubricating oils, have low biodegradability and can also be separated by agents such as polymer flocculants and inorganic salts. Because it is difficult to
There were major problems with wastewater treatment. As a solution to this problem, in addition to improving processing techniques using adsorbents and semipermeable membranes, attempts have been made to reduce the processing load of the lubricating oil itself. Part 1 of this attempt
One method is to solubilize polyether, which is essentially insoluble in water, with a surfactant and separate it by adding other surfactants or flocculants during wastewater treatment. Polyethers suitable for this method There are problems such as not having sufficient viscosity to be used as a lubricating oil, or due to changes in additives during use or contamination with metal ions and other impurities, the stability of the liquid deteriorates and it separates. It has not yet been put into practical use due to some problems. On the other hand, for water-based lubricating oils, methods are being considered to reduce the content of water-soluble polyethers and solvents and increase the water content, but this method has poor lubricity due to the large amount of water. Further, there were other problems such as a high pour point of about -5 to 0°C, making it unsuitable for use in winter, and it could not be used as a lubricating oil in practice. The present invention was made in order to eliminate the drawbacks of the conventional products as described above, and by using a specific polyether compound as an active ingredient, it has excellent lubricity and a low pour point, and it has excellent lubricity and low pour point. The purpose is to provide a lubricating oil that can be easily separated from water by dilution to recover the polyether component and has excellent drainage properties. The present invention is a lubricating oil containing a polyether compound represented by the following formula [ ] or [ ] as an active ingredient. _R ¹ _{_ _ _ _ _ _ _} ^{_ _} _{_ _ _ _} ) _n } (CpH _2p O) _o H ... [] (Here, R ¹ is a hydrocarbon group having 5 to 26 carbon atoms,
R ² and R ³ are each a hydrocarbon group having 1 to 26 carbon atoms, X is an oxygen atom or a nitrogen atom, p is 3 or 4, m is the average number of added moles of ethylene oxide from 1 to 30, l and n are carbon number 3 or 4
The average number of moles of alkylene oxide added is 0 to 40, respectively, and 2≦l+m+n≦90,
l/m and n/(l+m) are each 0 to 2, b is 1 or 2, and the numbers in { } indicate random addition or block addition in the stated order. ) In the present invention, the term "lubricating oil" refers to a conventionally used oil with lubricating properties, and includes water-based lubricating oils whose composition is water, and is generally used in hydraulic oils, metal processing, etc. oil, compressor oil,
It is used as drawing oil, heat transfer oil, etc. [In the formula], the hydrocarbon group represented by R ¹ includes pentyl group, hexyl group, heptyl group,
Octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, octadecyl group, eicosyl group, docosyl group, tetracosyl group, hexacosyl group, oleyl group, cyclopentyl group, cyclohexyl group , alkyl groups such as benzyl group, cinnamyl group, phenyl group, octylphenyl group, nonylphenyl group, dodecylphenyl group, naphthyl group, butylnaphthyl group, alkenyl group, cycloalkyl group, aryl-substituted alkyl group, aryl group, alkyl group There are substituted aryl groups, etc., and those with branches may be used. In the formula [], the hydrocarbon groups represented by R ² and R ³ include, in addition to the hydrocarbon groups exemplified as the hydrocarbon group for R ¹ , methyl group, ethyl group, propyl group, butyl group, allyl group. etc.,
It may have branches, and R ² and R ³ may be the same or different. In the [] formula or [] formula, (CpH _2p O)
Examples of the alkylene oxide having 3 or 4 carbon atoms include propylene oxide, butyl oxide, tetrahydrofuran, etc., and these may be added alone or in a mixed state. When the inside { } is a random addition, the entire inside { } acts as a hydrophilic chain, and when it is a block addition, the oxyethylene chain acts as a hydrophilic chain, and the inside { } acts as a hydrophilic chain.
An oxyalkylene chain having 3 or 4 carbon atoms added as a block to the outside acts as a hydrophobic chain. b indicates the number of substituents directly bonded to X, and is 1 when X is an oxygen atom and 2 when X is a nitrogen atom. The polyether compound of formula [] or [] uses an alcohol, phenol or amine having R ¹ , R ² or R ³ as a residue as a starting material, and ethylene oxide is added alone to this, or a polyether compound having 3 carbon atoms is used as a starting material. Alternatively, alkylene oxide of 4 (hereinafter simply referred to as alkylene oxide) and ethylene oxide are added randomly or in this order in a block manner, and if necessary, an alkylene oxide having 3 or 4 carbon atoms is further added in a block manner. Polyether compounds of formula [] or [] have excellent properties required for lubricating oils, such as lubricity, low-temperature fluidity, and stability, and are water-soluble, so they can be used alone or as a base for lubricating oils. I can,
When diluted, water separation properties improve, making wastewater treatment easy. In the [] formula or [] formula, the total number of added moles of ethylene oxide and alkylene oxide l+
m+n is limited to the range of 2 to 90 because 2
If it is less than that, it cannot be used as a lubricating oil component due to poor water solubility, or even if it is water soluble and has good water separation properties, it has a strong odor originating from the raw material alcohol or amine, which may be harmful to the environment, especially when used at elevated temperatures. In addition, if it exceeds 90, the content of alkyl groups in the molecule decreases too much, resulting in poor separability even when diluted with water. In this case, the number of moles of ethylene oxide added is selected from the range of 1 to 30, and the number of moles of alkylene oxide added is selected from the range of 0 to 40 for both the number of moles added first and the number of moles added in blocks afterward. . From the standpoint of wastewater treatment, the number of moles of ethylene oxide and alkylene oxide added is l + m + n.
The preferred range is 2 to 50, and the more preferred range is 2 to 30. In this case, the preferable range of the number m of added moles of ethylene oxide is 1 to
20, a more preferable range is 2 to 10, a preferable range of the number l of moles of alkylene oxide added first is 0 to 20, a further preferable range is 0 to 15, a preferable range of the number n of moles of alkylene oxide added later The range is 0 to 20, more preferably 0 to 10. The ratio l/m of alkylene oxide and ethylene oxide in { }, which acts as a hydrophilic chain, and the ratio n/(l+m) of hydrophobic chain and hydrophilic chain are both 0.
The reason why it is limited to 2 to 2 is because if it exceeds 2, the water solubility becomes poor and it cannot be used as a component of lubricating oil. The polyether compound of formula [] or [] has a hydrocarbon group having 5 to 26 carbon atoms or 1 to 26 carbon atoms, respectively, but R ¹ has 4 or less carbon atoms or R ² and R ³ have no hydrocarbon group. In some cases, the water solubility becomes so strong that it will not separate even if diluted with water, and no improvement in wastewater treatment performance can be expected.
Preferred hydrocarbon groups from the viewpoint of wastewater treatment properties are:
It has some degree of hydrophobicity, and even if ethylene oxide and/or alkylene oxide are added, its effect as a surfactant is weak, and the preferable range of carbon number is 5 to 20, more preferably 5 to 10. be. The lubricating oil of the present invention contains one or more polyether compounds represented by the formula [ ] or [ ] as an active ingredient, and one of the above compounds may be used alone as a lubricating oil, or it may be used as a lubricant in the composition. It can also be used as a lubricant in its form. Other ingredients in the composition include water, other solvents, other compounds of formula [ ] or [ ], other lubricating ingredients, and other additives. Among these, the water-based lubricating oil containing water as another component is preferably an aqueous solution containing 10% by weight or more of the lubricating component. Further, in the above lubricating oil composition, when lubricity is particularly required, a water-soluble compound having a number average molecular weight of 1,000 to 100,000 can be added as another lubricity component. In this case, if the number average molecular weight of the water-soluble compound is less than 1,000, it will not be effective in improving lubricity due to the low molecular weight, and if it exceeds 100,000, the shear stability will be extremely poor and the viscosity will decrease significantly under shear stress. undesirable. Examples of the water-soluble compounds include alginate, polyacrylate, maleic acid copolymer salt, polyacrylamide, water-soluble aniline resin, polyethyleneimine, vinylpyridine copolymer salt, polythiourea resin, polyvinyl alcohol, polyether, etc. However, polyethers having a strong affinity with the compound represented by the formula [] or [] are preferred. The polyether in this case is obtained by random or block addition polymerization of ethylene oxide and alkylene oxide to alcohols, phenols, amines, etc. having one or more active hydrogen atoms, and the molar ratio of ethylene oxide/alkylene oxide is 3/7. It is necessary that it is above. Moreover, it is preferable to have two or more terminal hydroxyl groups in order to improve the lubrication performance. Furthermore, if necessary, the water-soluble polyether may be made to have a high molecular weight using a coupling agent such as diisocyanate or diepoxide. When the water-soluble compound is used as a component of a water-based lubricating oil, the compound represented by the formula [] or [] is contained in an amount of 5 to 70% by weight, and the water-soluble compound is contained in an amount of 5 to 70% by weight.
It is desirable that the content is between 70% and 70% by weight. Water-based lubricating oil compositions containing water-soluble compounds have excellent low-temperature fluidity, but if it is necessary to further improve low-temperature fluidity, existing high-boiling point solvents can be added. High boiling point solvents include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol,
Examples include butanediol and hexylene glycol. The lubricating oil composition may contain other additives, such as an extreme pressure agent, an oiliness improver, an antifoaming agent, a rust preventive, and an antioxidant, if necessary. The lubricating oil of the present invention can be used both when the compound represented by the formula [] or [] as a component alone or in a composition with other components. Can be used for oil, metal processing oil, compressor oil, drawing oil, heat transfer oil, etc. Since the lubricating oil of the present invention has good miscibility with water, it is used in the form of an aqueous solution, and it may be mixed into cleaning water etc. and generate a large amount of waste water. When the compound mixed with water is further diluted several times to 1000 times with water, the polyether compound represented by the formula [] or [] will separate from the water, so it is usually used. Wastewater treatment can be easily carried out using a separation device such as a separator. In this way, the polyether component of the lubricating oil of the present invention can be separated and recovered by simply diluting it with water, but the separability can be further improved by adding a small amount of an inorganic coagulant that is normally used in wastewater treatment. I can do it. As described above, according to the present invention, since the specific polyether compound is used as an active ingredient, it has excellent lubricity, low-temperature fluidity, stability, etc., and is excellent in the general usage form of lubricating oil. In addition, it dissolves water within the range used as water-based lubricating oils, making it an excellent water-glycol flame-retardant hydraulic oil, cutting oil, grinding oil, press oil, and other water-soluble metal working oils. Moreover, since water separation properties can be improved by dilution, wastewater treatment is easy. Hereinafter, production examples and examples of the present invention will be described. Production example 1 Compound of the formula
After addition polymerization at 130℃ to 130℃ under pressure of 0.5 to 5.0Kg/ ^cm2 , propylene oxide was added under the same conditions.
Polyoxyethylene (3) oxypropylene (5) glycol monooctyl ether 27Kg (crude product) was obtained by addition polymerizing 14.5Kg (250mol) in the form of a block.
I got it. After neutralizing this crude product with an aqueous solution of potassium hydroxide and hydrochloric acid, it was dehydrated for 2 hours at 80 to 120°C under reduced pressure of 50 mmHg or less, and the precipitated salt was separated to obtain 26.5 kg of purified reaction product (sample No. 1). Ta. Production example 2 Compound of formula [] 15.7Kg of dipentylamine in a 300 volume airtight container
(100 mol), and add a mixture of 30.8 kg (700 mol) of ethylene oxide and 75.8 kg (1300 mol) of propylene oxide to 90 to
Polyoxyethylene (7), oxypropylene (13), and dipentylamine (sample No. 3) were subjected to random addition polymerization at 130°C under pressure of 0.5 to 5.0 Kg/ ^cm2 .
Obtained 122Kg. Various samples used in the following examples were manufactured according to the above manufacturing example. Example 1 A compound of the formula [] or [] shown in Table 1,
The kinematic viscosity, solubility in water, pour point, and odor were measured for a mixture of these with a water-soluble compound or water (inventive product), and a similar compound (comparative product). For a single compound, the solubility of the compound and water is 75:25 at 25℃.
(weight ratio) and judged whether it was uniformly dissolved or not, and for compositions, judged whether the composition was a homogeneous solution or not. In addition, odor was determined by a sensitivity test based on whether or not there was an odor. The results are shown in Table 1. In Tables 1 and 3, [],
[ ] indicates the formula [ ] or [ ], (block) and (random) indicate the type of addition polymerization in { }, EO indicates ethylene oxide, PO indicates propylene oxide, and BO indicates butylene oxide. Next, in Table 1, for the compositions that dissolve in water, 10 ml of the composition was diluted 10 times with water and left to stand at room temperature and 50°C, and when a flocculant was added and left to stand. The amount of separation after hours and the COD of the aqueous layer separated at room temperature were measured. The results are shown in Table 2. In Table 2, a 100 ml graduated separatory funnel (in units of 1 ml) was used to measure the amount of separation. In addition, COD was measured by the potassium permanganate method of JIS K-0102 industrial wastewater test method.

【table】

[Table] As is clear from the results in Table 1, the products of the present invention have excellent solubility in water, have a low pour point, and have a good odor (Samples No. 1 to 7), whereas the comparative products Disadvantages such as insolubility in water (Samples No. 9 and 12), high pour point (Sample No. 10), and odor (Sample No. 8) are observed. Next, from the results in Table 2, it can be seen that the product of the present invention exhibits excellent separation properties simply by diluting with water, while samples No. 8 and 10 of the comparative product are separated, but No. has a strong odor.
No. 10 has a small amount of separation, and No. 11 does not separate very well. In addition, the COD of the separated water is that of the comparative product with a strong odor.
Except for No. 8, the products of the present invention are extremely low compared to the comparative products. From the above results, it can be seen that the product of the present invention has excellent water solubility, low pour point, good odor, and excellent wastewater treatment properties. Example 2 The same tests as in Example 1 were conducted on a composition prepared by adding a high boiling point solvent and water to the compound of formula [] used in the present invention (product of the present invention) and a comparative product.
The results are shown in Tables 3 and 4. Among the comparative products, sample No.
Sample No. 15 is a general water-glycol formulation as a flame-retardant actuator, and sample No. 16 is a water-glycol formulation with a reduced amount of solvent and increased amount of water in order to reduce the wastewater treatment load. Sample No. 17 is an example of the base formulation of a general solution-type cutting oil.

【table】

【table】

[Table] According to the results in Tables 3 and 4, the product of the present invention has a low pour point, and when water is added, it is well separated from the aqueous layer, and the COD of the aqueous layer is also low, making wastewater treatment easy. Therefore, it can be seen that it is also useful as a water-glycol based flame-retardant hydraulic oil and a solution type cutting oil. On the other hand, comparative products No. 16 and 17 have a low content of organic matter in their compositions, so
The COD is somewhat low, but the disadvantage is that the pour point is high. Example 3 The product of the present invention and the currently commonly used water
In order to compare the lubrication performance of glycol-based flame-retardant hydraulic oil, sample No. 5 of Example 1 and Example 2 were used.
A pump test was conducted under the following test conditions on a composition in which 100 parts by weight of each sample No. 15 was blended with the following additives. (Additives) Oleic acid 5.0 parts by weight Potassium hydroxide 1.0 〃 Morpholine 0.5 〃 Benzotriazole 0.2 〃 (Pump test conditions) Hydraulic pump Vitsukas V-104C vane pump oil Volume 80 Set pressure 105Kg/cm ² Number of revolutions 1200rpm Oil temperature 50 ℃ Test time 100 hours The test results are shown in Table 5. In Table 5, the viscosity ratio is defined as the kinematic viscosity of the hydraulic oil before the test is _v1 , and the kinematic viscosity after the test is v1.
v ₂ , and the value is calculated using the following formula. Viscosity ratio = v ₂ / v ₁

[Table] As is clear from the results in Table 5, the product of the present invention showed no difference in lubricity compared to existing water-glycol-based flame-retardant hydraulic fluids, and It can be seen that it is excellent as

Claims (1)

[Claims] 1. A lubricating oil containing a polyether compound represented by the following formula [ ] or [ ] as an active ingredient. _R ¹ _{_ _ _ _ _ _ _} ^{_ _} _{_ _ _ _} ) _n }(CpH _2p O) _o H
...[] (Here, R ¹ is a hydrocarbon group having 5 to 26 carbon atoms,
R ² and R ³ are each a hydrocarbon group having 1 to 26 carbon atoms; Average number of moles added of 3 or 4 alkylene oxides, each from 0 to 40, 2≦l+m+n≦90, l/m
and n/(l+m) are respectively 0 to 2, b
is 1 or 2, and the numbers in { } indicate random addition or block addition in the order of description. ) 2 R ¹ , R ² and R ³ are hydrocarbon groups having 5 to 20 carbon atoms, m is 1 to 20, l and n are each 0 to 20, and 2≦l+m+n≦50, Claim 1 Lubricating oil as described in section. 3 Claims in which R ¹ , R ² and R ³ are hydrocarbon groups having 5 to 10 carbon atoms, m is 2 to 10, l is 0 to 15, n is 0 to 10, and 2≦l+m+n≦30 The lubricating oil according to item 1. 4. The lubricating oil according to any one of claims 1 to 3, wherein the lubricating oil is an aqueous solution. 5. The lubricating oil according to claim 4, wherein the lubricating oil further contains a water-soluble compound having a number average molecular weight of 1,000 to 100,000. 6. The lubricating oil according to claim 5, which contains 5 to 70% by weight of a polyether compound represented by formula [] or formula [] and 5 to 50% by weight of a water-soluble compound. 7. The lubricating oil according to claim 5 or 6, wherein the water-soluble compound is polyether. 8. The lubricating oil according to any one of claims 4 to 7, wherein the lubricating oil is a hydrous hydraulic oil.