JPH075905B2 - Flame retardant lubricant - Google Patents

Description

TECHNICAL FIELD The present invention relates to a flame-retardant lubricating oil.

(Prior Art) Conventionally, as a flame retardant lubricant, a water-glycol type, a phosphoric acid ester type, an emulsion type, a fatty acid ester type and the like are known in hydraulic oils. Emulsions, solves and chemical solutions in cutting oils also belong to flame retardant lubricants.

Conventionally, it has been possible to make a lubricant flame-retardant by including about 10% or more of water in the system. Also,
Flame retardation is possible by adding a halogen such as phosphoric acid ester, fatty acid ester, chlorine and fluorine, or by adding a halogenated compound.
Some of these substances have flash points and cannot be non-hazardous substances under the Fire Service Law. From the concept of non-dangerous substances that do not have a flash point, it is the easiest method to include water in an organic substance in an amount of about 10% or more, preferably about 15% or more,
This is a known method.

(Problems to be solved by the invention) Conventionally, these flame-retardant lubricants are produced by mixing and dissolving a water-soluble organic substance and water, or by using an emulsifier to disperse mineral oil in water or water in mineral oil. However, the biggest problem with these flame-retardant lubricants is the infinite water dissolution in the system. For example, lubricants such as gear oil are used in rolling parts of hot steel rolling mills and their peripheral equipment. However, since this part is constantly exposed to a large amount of cooling water during rolling, a general water-glycol system is used. As described above, a substance that can be dissolved in water without limitation cannot be a stable gear oil because the capacity and performance vary depending on the mixed water. In addition, when the lubricant dissolves water indefinitely, there is a problem in that when the lubricant diluted with water is discarded, the waste water treatment requires a great deal of expense.

The conventional water-based lubricant has a problem that it cannot dissolve mineral oil. Many of the lubricating oil additives have been developed for lubricating oils made of mineral oil, and cannot be applied to conventional water-based lubricating oils. For example, even if a water-glycol hydraulic oil is used as a gear oil, additives such as sulfurized olefins and phosphoric acid esters cannot be dissolved and the same extreme pressure property as that of existing mineral oil gear oils cannot be imparted. Further, since water-glycol type hydraulic oil does not dissolve mineral oil, it takes a lot of time and cost for flushing work to completely remove the previous oil.

(Means for Solving Problems) The inventors of the present invention have conducted various studies to obtain a lubricant without the above-mentioned conventional flame-retardant lubricants, and as a result, an aqueous composition having a specific composition is excellent. They have found that they have characteristics, and completed the present invention.

That is, the gist of the present invention is (A) a polyoxyalkylene glycol diether 5 represented by the following general formula (I).
To 85% by weight, (B) 5 to 50% by weight of glycol monoether represented by the following general formula (II), (C) 5 to 30% by weight of polyoxyalkylene glycol monoether represented by the following general formula (III), (D) 1 to 50% by weight of a mineral oil base oil and (E) 10 to 50% by weight of water, a flame-retardant lubricating oil R ₁ -G ₁ -O-R ₃ -G ₂ -O- R ₄ (I) (wherein R ₁ and R ₄ are monovalent hydrocarbon groups having 6 to 30 carbon atoms, G ₁ ,
G ₂ is a polyoxyalkylene group composed of a copolymer of an oxyethylene group and an oxypropylene group and / or an oxybutylene group, R ₃ is a methylene group or an ethylene group, and is composed of an oxyethylene group and a higher oxyalkylene group. The weight ratio is 10/90 to 80/20 and the average molecular weight is in the range of 500 to 20000. _{) R 5 -OC 2 H 4 OeH} (II) ( wherein R ₅ is a monovalent hydrocarbon group having 1 to 8 carbon atoms, e is a number from 1 or _{2.) R 6 -G 3 -OH} ( III) (wherein R ₆ is a monovalent hydrocarbon group having 6 to 30 carbon atoms, G ₃ is a polyoxyethylene group, or a copolymer of an oxyethylene group and an oxypropylene group and / or an oxybutylene group) It represents a polyoxyalkylene group, and the number of oxyethylene group units is 3 to 30, and the number of oxypropylene group and oxybutylene group units is 0 to 40).

Since the lubricating oil of the present invention can contain a sufficient amount of water in the composition, it exhibits flame retardancy, and there is a limit to the amount of water that can be contained in this composition, and more water can be mixed in. Even if it is done, it has a characteristic that it is not absorbed into the composition and is removed from the system as it is, and that this lubricating oil has a characteristic that it is essentially insoluble in water, and that it also dissolves mineral oil. .

The derivative of polyoxyalkylene glycol used in the present invention is represented by the above-mentioned general formulas (I), (II) and (III), and by mixing them, water and a mineral base oil are stably contained. be able to. The above formulas (I) and (II
In the polyoxyalkylene groups G ₁ , G ₂ , and G ₃ of I), the oxyethylene group portion and the higher oxyalkylene group portion may form a random copolymer or a block copolymer.

As the polyoxyalkylene glycol diether represented by the formula (I), those represented by the following formula (I a) or (I b) are preferable.

_{R 1 -OR 2 -OaC 2 H 4} ObR 3 OC 2 H 4 cO -R 2) d-O-R 4 (I a) R 1 -OC 2 H 4 ObR 2 -OaR 3 O -R 2) dOC 2 H ₄ cO-R ₄ (I b) In the above formulas (I a) and (I b), R ₁ and R ₄ are monovalent linear or branched saturated or unsaturated aliphatic, alicyclic or aromatic carbon R ₁ which is a hydrogen group and has 6 to 30 carbon atoms
And R ₄ may be the same or different, and examples thereof include hexyl group, hexenyl group, octyl group, nonyl group, decyl group, dodecyl group, hexadecyl group, octadecyl group, oleyl group, benzyl group, phenyl group, Examples include tolyl group, hexylphenyl group, xylyl group, cyclohexyl group, octylcyclohexyl group and the like. R ₂ O represents an oxypropylene group, an oxybutylene group, or a mixed group thereof, and R ₃ represents a methylene group or an ethylene group. a, b, c,
d represents a positive integer. The weight ratio of the oxyethylene group and the higher oxyalkylene group R ₂ O is about 10/90 to 80/20.
Especially, those of about 20/80 to 60/40 are preferable. The oxyethylene group portion and the higher oxyalkylene group portion form a block copolymer with each other. Formula (I a), (I b)
The average molecular weight of the compound is about 500 to 20000.

The polyoxyalkylene glycol diethers of the above formulas (I), (Ia), and (Ib) can retain a certain amount of water, but have the characteristic that even if more water is mixed in, they are excluded from the system. Have Here, when the number of carbon atoms of the hydrocarbon groups R ₁ and R ₄ in the above formulas (I), (I a) and (I b) is less than 6, the water solubility becomes strong and the composition itself becomes easily soluble in water, If the number is more than 30, the water-storability of the composition will be lost.

Here, the oxyethylene group and the oxyalkylene group R ₂ O
The ratio with is limited when the ratio is smaller than 10/90, the saturated water content becomes extremely small, and when it is larger than 80/20, the water solubility becomes large and it becomes difficult to contain the mineral base oil. This is because. Further, the compounds of the formulas (I), (I a) and (I b) easily evaporate when the molecular weight is less than about 500, the viscosity of the composition becomes too low, and the molecular weight is about 20.
If it exceeds 000, the viscosity will be too high, which will hinder circulation work. Further, when the compounding amount of the polyoxyalkylene glycol diether of the formulas (I), (I a) and (I b) becomes too small, the property of keeping the saturated water content within a certain limit is impaired, and the lubricity (viscosity) When the amount of water is too small, flame retardancy is impaired.

The compounds of the formulas (I), (I a) and (I b) are described in, for example, JP-A-48 / 48
-22198 and Japanese Patent Publication No. 49-15185 can be used for the production. That is, propylene oxide and / or butylene oxide is addition-polymerized to alcohol or phenol of R ₁ OH, and then ethylene oxide is addition-polymerized to obtain polyoxyalkylene glycol monoether, to which sodium alkoxide is added to give 80% in an inert gas. It can be prepared by a method of heating and mixing at ˜150 ° C. and gradually adding methylene dihalide or ethylene dihalogenate to the product to react, and adding R ₁ OH alcohol or phenol to propylene oxide and / or
Or butylene oxide addition polymerization, then ethylene oxide addition polymerization, then propylene oxide and / or
Alternatively, it can also be prepared by addition polymerization of butylene oxide to obtain polyoxyalkylene glycol monoether and etherification of the terminal OH group.

The second component (B) of the flame-retardant lubricating oil according to the present invention is represented by the following general formula (II).

R ₅ —OC ₂ H ₄ OeH (II) In the formula, R ₅ is a monovalent linear or branched, saturated or unsaturated aliphatic, alicyclic or aromatic hydrocarbon group having 1 to 8 carbon atoms,
Examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a hebutyl group, an octyl group, an octenyl group, a benzyl group, a tolyl group, a xylyl group, and a cyclohexyl group, and e represents a number of 1 or 2. By adding this compound to the compounds of the above formulas (I), (Ia) and (Ib), it is possible to reduce the fluctuation of the water content possible with respect to temperature, and when a large amount of externally mixed water is contained. The gelation tendency of can be prevented. It is necessary to prevent gelation especially when a mineral oil base oil is blended.

As the polyoxyalkylene glycol monoether represented by the above formula (III), those represented by the following formula (IIIa) are preferable.

R ₆ —OR ₂ —OfC ₂ H ₄ OgR ₂ —OhH (IIIa) In the above formula (IIIa), the group R ₆ is represented by the formula (I), (Ia), (I
The same groups as the groups R ₁ and R ₄ of the compound of b) can be used, and the group R ₂ O
The same groups as the groups R ₂ O in formulas (I a) and (I b) can also be used. That is, the group R ₆ is a monovalent linear or branched saturated or unsaturated aliphatic, alicyclic or aromatic hydrocarbon group having 6 to 30 carbon atoms, such as a hexyl group, a hebutyl group, an octyl group, an octenyl group or dodecyl. Group, octadecyl group, benzyl group, tolyl group, xylin group, cyclohexyl group, etc., f is an integer of 0 to 10, g is an integer of 3 to 30, and h is 0.
Represents an integer of ˜30, and the oxyethylene group and the higher oxyalkylene group moiety form a block copolymer with each other or a homopolymer having only an oxyethylene group. When the carbon number of R ₆ is small, f, g,
h may be a small integer, but when R ₆ has a large number of carbon atoms, f, g, and h are 3 or less, it is necessary to use a large integer because water is not dissolved. However, if the respective upper limits are exceeded, gelation occurs and the product cannot be used. The addition of the compound of formula (III) or (IIIa) to the compound of formulas (I) or (Ia), (Ib) and (II) above facilitates dissolution of the mineral base oil. The compounds of formulas (III) and (IIIa) are represented by formulas (I) and (I
It can be prepared according to the method for preparing the compounds of a) and (Ib).

The composition of the flame-retardant lubricating oil according to the present invention (total 100%) is about 5 to 85% by weight, preferably about 20 to about 20% by weight of the compound of the above formula (I), (Ia) or (Ib). 60% by weight, about 5 to 50% by weight of the compound of the above formula (II), preferably about 5 to 30% by weight, about 5 to 30 of the compound of the above formula (III) or (IIIa)
% By weight, preferably about 5-20% by weight, about 1-mineral oil base oil
50% by weight, preferably about 10-40% by weight, and about 5% water.
It comprises 50% by weight, preferably about 10-50% by weight. In this mixture, particularly in a mixture containing a large amount of a high-viscosity mineral base oil, if the composition of the formula (II) is too small, external mixing water causes gelation at low temperature, and if it is too large, the viscosity is lowered. There is no particular limitation on the mineral oil base oil, and various flammability ranges such as about 1 cSt / 40 depending on the required viscosity.
It can be used in the range of ℃ ~ 1000cSt / 40 ℃. Water imparts flame retardancy and cooling properties to the lubricating oil of the present invention, and mineral oil facilitates the dissolution of mineral oil-based additives and increases the viscosity of the composition.

The flame-retardant lubricating oil according to the present invention can be used satisfactorily even if it comprises only the basic composition, but it may further contain other thickeners, diluent additives and the like.

One example of a suitable thickener or diluent is a polyoxyalkylene compound that has been conventionally compounded in conventional hydraulic oils and brake oils. Examples include polyoxypropylene glycol, its monoethers or diethers,
Poly (oxyethylene-oxypropylene) glycol copolymer, its monoether or diether, poly (oxyethylene-oxybutylene) glycol copolymer, its monoether or diether, polyoxypropylenetriol, poly (oxyethylene-oxypropylene) triol, sorbitol Examples thereof include those obtained by addition-polymerizing propylene oxide or a mixed alkylene oxide of propylene oxide and ethylene oxide to a polyhydric alcohol such as. These polyoxyalkylene compounds are monohydric alcohols such as methanol and ethanol, polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin and sorbitol, phenols, amines and other compounds having active hydrogen, and propylene oxide and / or butylene oxide. Alternatively, it is produced by addition-polymerizing a mixture of these alkylene oxides and ethylene oxide, and the terminal OH group is etherified if necessary. When blending these polyoxyalkylene compounds with the flame-retardant lubricating oil according to the present invention, it is particularly advantageous to use a water-insoluble one from the viewpoint of wastewater treatment. A weight ratio of about 50/50 or less to the oxypropylene group portion and / or the oxybutylene group portion is suitable. The copolymer may be a random copolymer or a block copolymer. When these polyoxyalkylene compounds are blended as a thickener or a bulking agent, those having a molecular weight of about 500 or more, particularly about 1000 to 50,000 are preferable. In order not to impair the water retention within a certain limit and the flame retardancy, which are features of the lubricating oil of the present invention, the amount of these thickeners or extenders and diluents to be added is about 30% by weight in the lubricating oil composition of the present invention. % Or less is suitable.

To the lubricating oil of the present invention, an additive such as a normal lubricant, an antioxidant, an anticorrosive, an anticorrosive, an antifoaming agent, a pour point depressant, and a viscosity index improver can be added if necessary. . Any lubricant can be used as long as it can be dissolved in the composition of the present invention, and examples thereof include fatty acids such as palmitic acid, stearic acid and oleic acid, lard oil, olive oil,
Fats and oils such as castor oil and rapeseed oil, higher alcohols,
Higher fatty acid esters, synthetic lubricating oils, tricresyl phosphate, trixylenyl phosphate, monooctyl phosphate, dioctyl phosphate, trioctyl phosphate, trioctyl phosphite, trioctyl thiophosphate, phosphodiesters such as tricresyl thiophosphate. , Phosphorus-containing additives such as phosphites and thiophosphates, phosphorus-based ester amine salts in which residual OH groups of these phosphorus-based additives are neutralized with amines, hydrocarbon sulfides such as dioctyl polysulfide and terpene sulfides s, terpenes and C ₅ ~ ₂₀ unsaturated hydrocarbon and phosphorus sulfide _{(P 2 S 5, P 2} S 4 , etc.) is the reaction product of a sulfur - phosphorus-based additive, a zinc dialkyldithiophosphate, chlorinated paraffin Chlorinated hydrocarbon additives such as, sulfurized fats and oils, sulfide additives such as mineral oil, dimer acid amide Which fatty acid amides, amine oleate, potassium oleate, aluminum stearate,
Fatty acid soaps such as copper naphthenate and lead stearate,
Solid lubricants such as molybdenum disulfide and graphite (solid lubricants do not dissolve but disperse. Used in gear oils and cutting oils) Sulfur chloride-based additives that combine sulfur chloride with fatty oils. Lubricants (oiliness improvers, antiwear agents, extreme pressure agents) that are particularly suitable for hydraulic oils and gear oils are fatty acids,
Fatty acid soaps, sulfur-based additives, phosphorus-based additives, sulfur-phosphorus-based additives, zinc-based additives, fats and oils, and additives particularly suitable for cutting oil are sulfur-based additives and chloride-based additives among the above. Additives, fatty acids, fats and oils, fatty acid soaps, phosphorus-based additives. Any rust preventive and anticorrosive may be used as long as they are soluble in the composition of the present invention, and examples thereof include rosins such as abietic acid, ethanolamines, benzothiazoles, benzotriazoles, amines, amides, Carboxylic acid soaps such as lead naphthenate and aluminum stearate, sulfonic acid soaps such as calcium sulfonate and barium sulfonate, sulfonates, naphthenates, alkenyl succinic acids, polyoxyalkylene alkyl ethers, polyoxyalkylene alkylphenol ethers , Sorbitan fatty acid esters, polyoxyalkyl sorbitan fatty acid esters,
There are nonionic surfactants such as polyoxyalkyl esters. Examples of antioxidants include methylene-4,
Examples include bisphenols such as 4-bis (2,6-ditertiary butylphenol), alkylphenols such as ditertiary butylcresol, naphthylamines, zinc diallyl dithiophosphates. Examples of the defoaming agent include a silicone defoaming agent and a polymethylmethacrylate defoaming agent. The amount of lubricant added is usually about 1-30
%, Particularly about 1 to 15% by weight, the amount of rust / corrosion inhibitor added is about 1 to 15% by weight, and the amount of antioxidant and defoamer added is about 0.001 to 1% by weight, respectively. .

(Effects of the Invention) The first characteristic of the lubricating oil of the present invention is that a certain amount of water can be contained in the composition, but no more water can be contained in the system, and it is hardly dissolved in water. is there. The insolubility in water provides a significant benefit, i.e., common water-glycol based hydraulic oils make wastewater treatment difficult due to their unlimited solubility in water, whereas the lubricating oils of the present invention are water soluble. This is because even if a large amount of waste water is mixed in for separation, it is possible to separate and collect as easily as ordinary mineral oil alone. In addition, the property that a certain amount of water or more cannot be contained in the system and is discharged to the outside of the system is, for example, that flame retardant lubricants such as gear oil used in rolling parts of hot steel rolling mills and peripheral equipment It has an extremely excellent effect on That is,
This is because the performance does not change due to the mixed water. The second feature of the lubricating oil of the present invention is that a certain amount of mineral oil base oil can be transparently dissolved in the system. The feature of dissolving mineral oil has the effect that additives used in lubricating oils composed of ordinary mineral oil can be freely selected. Further, the lubricating oil of the present invention can contain not only mineral oil in the system but also a certain amount of mineral oil from outside the system can be dissolved. This is
When the conventional lubricating oil composed of mineral oil is replaced with the lubricating oil of the present invention for the purpose of making it flame-retardant, it is not necessary to completely remove the previous history oil slightly remaining in the apparatus, and it is easy to change the oil.

The lubricating oil of the present invention does not show a flash point and does not correspond to a dangerous substance under the Fire Service Law. It also has the characteristics of a large specific heat and a large heat transfer coefficient, a low pour point, and excellent resistance to shearing. And for example,
Smoke emission, which is a problem when used as cutting and grinding oil, is low. Therefore, the lubricating oil of the present invention has an advantage that it can be commonly used in many applications. That is, a single oil type can be commonly used as hydraulic oil, industrial gear oil, cutting and grinding oil. The common use of a single type of lubricating oil for many kinds of applications is currently strongly demanded in the industry, but the lubricating oil of the present invention is used as, for example, a hydraulic oil and a cutting / grinding oil, or a hydraulic oil. A single type of oil can be commonly used as the oil and the gear oil, and the above-mentioned industrial requirements can be met.

(Example) The characteristics of the lubricating oil of the present invention will be specifically described with reference to the following examples.

In the following examples, EO represents an oxyethylene group, PO represents an oxypropylene group, and BO represents an oxybutylene group.
Unless otherwise specified,% means% by weight.

Examples 1 to 7 and Comparative Examples 1 to 3 Examples according to the present invention have the compositions shown in Table 1, Examples 1 and 2,
4 is an example of the flame-retardant gear oils of 4, 5, 6, 7 and the flammable hydraulic oil of Example 3. The flame-retardant gear oil in this example does not show a flash point, and as shown in the performance in Table 2, it has an extreme pressure property equal to or higher than that of the ordinary mineral oil type commercial gear oil A (Comparative Example 1). Further, since the flame-retardant gear oils shown in the examples may contain a few% of mineral oil from outside the system, the flushing operation could be omitted when renewing from the mineral oil-based commercial gear oil A.

The flame-retardant hydraulic oil shown in Example 3 has no flash point and a viscosity of 46.
cSt / 40 ℃, pour point -30 ℃, showing the property of ASTM-D-2882
V-104C vane pump test specified to -70T 140kg / cm ² ,
The total wear amount of the cam ring and vane after 1200 rpm and 1000 hours was 100 mg, and the commercially available water glycol hydraulic oil B (Comparative Example 2) carried out for comparison was 40 mg in total under the same conditions and the commercial water glycol hydraulic oil C ( Comparative example 3) shows a total wear amount of 1000 mg
showed that.

Reference Example 1 The polyoxyalkylene glycol dieers used in Examples 1, 6 and 7 were produced by the following method.

187 g of dodecanol and 4.5 g of KOH were charged in an autoclave of 3 and dehydrated at a vacuum degree of 30 mmHg or less and a temperature of 100 to 120 ° C., and 682 g of propylene oxide was charged at a temperature of 100 to 120 ° C., and after sufficient reaction, degassing was performed. Charge 576 g of ethylene oxide at 110-140 ° C. Ethylene oxide,
During the reaction of propylene oxide, the reaction was carried out in N ₂ gas so that the gauge pressure of the autoclave was adjusted to 5 kg / cm ² or less. After the reaction of ethylene oxide has progressed sufficiently 30
Degassing is performed at a vacuum degree of mmHg or less and a temperature of 80 to 100 ° C. to obtain 1416 g of a reactant. Sodium methylate (52 g) was added to the reaction product (1000 g) and reacted at a temperature of 130 ° C to 140 ° C for 6 hours to prepare an alcoholate.
The reaction was carried out at ℃ for 3 hours to obtain 970 g of a reaction product. The by-produced inorganic salt was removed from this reaction product to obtain 873 g of polyoxyalkylene glycol diether.

Reference Example 2 The polyoxyalkylene glycol diether used in Example 2 was produced by the following method.

Tetradecanol (215 g) and KOH (4.1 g) were charged into an autoclave of 3 and dehydrated at a vacuum degree of 30 mmHg or less and a temperature of 100 to 120 ° C, and 604 g of propylene oxide was charged at a temperature of 100 to 120 ° C, and after sufficient reaction, degassing was performed. Then, 518 g of ethylene oxide is charged at 110 to 140 ° C. During the reaction of ethylene oxide and propylene oxide, the reaction was carried out in N ₂ gas so that the gauge pressure of the autoclave was adjusted to 5 kg / cm ² or less. After the reaction of ethylene oxide proceeds sufficiently, degassing is performed at a vacuum degree of 30 mmHg or less and a temperature of 80 to 100 ° C. to obtain 1280 g of a reaction product. To 1000 g of this reaction product, 55 g of sodium methylate was added and reacted at a temperature of 130 ° C to 140 ° C for 6 hours to form an alcoholate.
The reaction was carried out at 0 to 120 ° C. for 3 hours to obtain 971 g of a reaction product. The by-produced inorganic salt was removed from this reaction product to obtain 872 g of polyoxyalkylene glycol diether.

Reference Example 3 The polyoxyalkylene glycol diether used in Example 3 was produced by the following method.

Tetradecanol (430 g) and KOH (4.8 g) are charged into an autoclave of 3 and dehydrated at a vacuum degree of 30 mmHg or less at a temperature of 100 to 120 ° C, and 604 g of propylene oxide at a temperature of 100 to 120 ° C, and after sufficient reaction, degassing is performed. Then, add 564g of ethylene oxide at 110-140 ℃. During the reaction of ethylene oxide and propylene oxide, the reaction was carried out in N ₂ gas so that the gauge pressure of the autoclave was adjusted to 5 kg / cm ² or less. After the reaction of ethylene oxide proceeds sufficiently, degassing is performed at a vacuum degree of 30 mmHg or less and a temperature of 80 to 100 ° C. to obtain 1568 g of a reaction product. To 1000 g of this reaction, 90 g of sodium methylate was added and reacted at a temperature of 130 ° C to 140 ° C for 6 hours to make an alcoholate.
The reaction was carried out at -120 ° C for 3 hours to obtain 975 g of a reaction product. The by-produced inorganic salt was removed from this reaction product to obtain 877 g of polyoxyalkylene glycol diether.

Reference Example 4 The polyoxyalkylene glycol diether used in Example 4 was produced by the following method.

19 g of dodecanol and 3.2 g of KOH were charged into an autoclave of 3 and dehydrated at a vacuum degree of 30 mmHg or less and a temperature of 100 to 120 ° C.
830 g of propylene oxide is charged at a temperature of 100 to 120 ° C, degassing is performed after sufficient reaction, and 235 g of ethylene oxide is charged at 110 to 140 ° C. During the reaction of ethylene oxide and propylene oxide, the reaction was carried out in N ₂ gas so that the gauge pressure of the autoclave was adjusted to 5 kg / cm ² or less. After the reaction of ethylene oxide has progressed sufficiently, 30
Degassing is performed at a vacuum degree of mmHg or less and a temperature of 80 to 100 ° C. to obtain 1062 g of a reactant. Sodium methylate (8 g) was added to this reaction product (1000 g) and reacted at a temperature of 130 ° C to 140 ° C for 6 hours to form an alcoholate, which was then heated to 100 ° C to 120 ° C with methylene chloride.
And reacted for 3 hours to obtain 960 g of a reaction product. The by-produced inorganic salt was removed from this reaction product to obtain 858 g of polyoxyalkylene glycol diether.

Reference Example 5 The polyoxyalkylene glycol diether used in Example 5 was produced by the following method.

187 g of dodecanol and 4.0 g of KOH were charged into an autoclave of 3, dehydrated at a vacuum degree of 30 mmHg or less and a temperature of 100 to 120 ° C, and 648 g of 1,2-butylene oxide was charged at a temperature of 100 to 120 ° C. After sufficient reaction, degassing was performed. Then, 518 g of ethylene oxide is charged at 110 to 140 ° C. During the reaction of ethylene oxide and 1,2-butylene oxide, the reaction was carried out in N ₂ gas so that the gauge pressure of the autoclave was adjusted to 5 kg / cm ² or less. After the reaction of ethylene oxide proceeds sufficiently, degassing is performed at a vacuum degree of 30 mmHg or less and a temperature of 80 to 100 ° C. to obtain 1325 g of a reaction product. To 1000 g of this reaction product, 59 g of sodium methylate was added and reacted at a temperature of 130 to 140 ° C. for 6 hours to form an alcoholate, which was reacted with methylene chloride at a temperature of 100 to 120 ° C. for 3 hours to obtain 965 g of a reaction product. The inorganic salt produced as a by-product was removed from this reaction product to obtain 869 g of polyoxyalkylene glycol diether.

Reference Example 6 The polyoxyalkylene glycol monoether used in Examples 1, 4, and 5 was produced by the method described below.

Dodecanol 243g and KOH 4.0g were charged into an autoclave of 3 and dehydrated at a vacuum degree of 30mmHg or less and a temperature of 100 to 120 ° C, and 393g of propylene oxide was charged at a temperature of 100 to 120 ° C, and after sufficient reaction, degassing was performed, Further, 735 g of ethylene oxide is charged at 110 to 140 ° C. Ethylene oxide,
During the reaction of propylene oxide, the reaction was carried out in N ₂ gas so that the gauge pressure of the autoclave was adjusted to 5 kg / cm ² or less. After the reaction of ethylene oxide has progressed sufficiently,
Degassing is performed at a vacuum degree of 30 mmHg or less and a temperature of 80 to 100 ° C. to obtain 1335 g of a reaction product. This reaction product was neutralized with hydrochloric acid to remove by-produced salts and water, and 1302 g of polyalkylene glycol monoether was obtained.

Reference Example 7 The polyoxyalkylene glycol monoether used in Example 2 was produced by the following method.

540g of higher linear alcohol with an average carbon number of 18 and KOH3.5g 3
Charged in an autoclave at a vacuum degree of 30 mmHg or less, 100
Dehydrate at a temperature of ~ 120 ° C and add 754g of ethylene oxide to 100g.
Charge at a temperature of ~ 120 ° C. During the reaction of ethylene oxide, the reaction is carried out in N ₂ gas and the gauge pressure of the autoclave is 5 kg /
It was adjusted to be cm ² or less. After the reaction of ethylene oxide has proceeded sufficiently, the vacuum degree of 30 mmHg or less, 80-100
Degassing is carried out at a temperature of ° C to obtain 1260 g of the reaction product. This reaction product was neutralized with hydrochloric acid to remove by-produced salt and water, and 1225 g of polyalkylene glycol monoether was obtained.

Reference Example 8 The polyoxyalkylene glycol monoether used in Example 3 was produced by the following method.

279 g of dodecanol and 4.1 g of KOH were charged into an autoclave of 3 and dehydrated at a vacuum degree of 30 mmHg or less and a temperature of 100 to 120 ° C., and 339 g of propylene oxide was charged at a temperature of 100 to 120 ° C., and after sufficient reaction, degassing was performed. Charge 636 g of ethylene oxide at 110-140 ° C. Ethylene oxide,
During the reaction of propylene oxide, the reaction was carried out in N ₂ gas so that the gauge pressure of the autoclave was adjusted to 5 kg / cm ² or less. After the reaction of ethylene oxide has progressed sufficiently,
Degassing is performed at a vacuum degree of 30 mmHg or less and a temperature of 80 to 100 ° C to obtain 1228 g of a reaction product. The reaction product was neutralized with hydrochloric acid to remove by-produced salts and water, and 1190 g of polyalkylene glycol monoether was obtained.

Reference Example 9 The polyoxyalkylene glycol monoether used in Example 6 was produced by the following method.

130 g of octanol and 3.3 g of KOH were charged into an autoclave of 3 and dehydrated at a vacuum degree of 30 mmHg or less and a temperature of 100 to 120 ° C., and 603 g of propylene oxide was charged at a temperature of 100 to 120 ° C., and after sufficient reaction, degassing was performed. Charge 376 g of ethylene oxide at 110-140 ° C. Ethylene oxide,
During the reaction of propylene oxide, the reaction was carried out in N ₂ gas so that the gauge pressure of the autoclave was adjusted to 5 kg / cm ² or less. After the reaction of ethylene oxide has progressed sufficiently,
Degassing is performed at a vacuum degree of 30 mmHg or less and a temperature of 80 to 100 ° C. to obtain 1085 g of a reaction product. The reaction product was neutralized with hydrochloric acid to remove by-produced salts and water, and 1050 g of polyalkylene glycol monoether was obtained.

Reference Example 10 The polyoxyalkylene glycol monoether used in Example 7 was produced by the following method.

Charge 150 g of dodecanol and 5.0 g of KOH into an autoclave of 3 and dehydrate at a vacuum degree of 30 mmHg or less and a temperature of 100 to 120 ° C. Charge 242 g of propylene oxide at a temperature of 100 to 120 ° C, degas after sufficient reaction, and further Charge 376 g of ethylene oxide at 110-140 ° C and after sufficient reaction, charge 905 g of propylene oxide at 100-120 ° C. During the reaction of ethylene oxide and propylene oxide, the reaction was carried out in N ₂ gas so that the gauge pressure of the autoclave was adjusted to 5 kg / cm ² or less. After the reaction of propylene oxide has sufficiently proceeded, degassing is performed at a vacuum degree of 30 mmHg or less and a temperature of 80 to 100 ° C to obtain 1640 g of a reaction product. The reaction product was neutralized with hydrochloric acid to remove by-produced salts and water, and 1585 g of polyalkylene glycol monoether was obtained.

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Claims (1)

[Claims] (A) 5 to 85% by weight of a polyoxyalkylene glycol diether represented by the following general formula (I):
(B) 5 to 50% by weight of glycol monoether represented by the following general formula (II), (C) Polyoxyalkylene glycol monoether 5 represented by the following general formula (III)
A flame-retardant lubricating oil comprising 30 to 30% by weight, (D) 1 to 50% by weight of a mineral oil base oil, and (E) 10 to 50% by weight of water. R ₁ —G ₁ —O—R ₃ —G ₂ —O—R ₄ (I) (wherein R ₁ and R ₄ are monovalent hydrocarbon groups having 6 to 30 carbon atoms, G ₁ ,
G ₂ is a polyoxyalkylene group composed of a copolymer of an oxyethylene group and an oxypropylene group and / or an oxybutylene group, R ₃ is a methylene group or an ethylene group, and is composed of an oxyethylene group and a higher oxyalkylene group. The weight ratio is 10/90 to 80/20 and the average molecular weight is in the range of 500 to 20000. _{) R 5 -OC 2 H 4 OeH} (II) ( wherein R ₅ is a monovalent hydrocarbon group having 1 to 8 carbon atoms, e is a number from 1 or _{2.) R 6 -G 3 -OH} ( III) (wherein R ₆ is a monovalent hydrocarbon group having 6 to 30 carbon atoms, G ₃ is a polyoxyethylene group, or a copolymer of an oxyethylene group and an oxypropylene group and / or an oxybutylene group) It represents a polyoxyalkylene group, and the number of oxyethylene group units is 3 to 30, and the number of oxypropylene group and oxybutylene group units is 0 to 40.)