JPH0668111B2 - Hydrous lubricant - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a water-containing lubricant, and more particularly to a water-containing lubricant having high corrosion resistance and excellent wear resistance. This water-containing lubricant can be effectively used as a hydraulic fluid, a metal working fluid for rolling and drawing, a heat treatment fluid, and the like.

[Problems to be Solved by Prior Art and Invention]

Conventionally, as a water-containing lubricant, a lubricant containing a polymer compound such as polyvinyl alcohol or polyalkylene glycol has been used for the purpose of increasing the viscosity of the lubricant and improving the lubricating performance.

However, this lubricant has drawbacks such as insufficient wear resistance, low pH of the lubricant, and insufficient corrosion resistance.

The first object of the present invention is to provide a water-containing lubricant in which these conventional drawbacks are eliminated.

A second object of the present invention is to provide a water-containing lubricant having a further excellent gelation preventing effect together with the above.

[Means for solving problems]

That is, the present invention is, firstly, (A) an α-olefin having 2 to 12 carbon atoms, (B) styrene, vinyl chloride, vinyl acetate,
At least one vinyl compound selected from the group consisting of vinyl propionate, acrylonitrile, alkyl vinyl ether, and acrylic acid ester, and (C) maleic acid or a derivative thereof are prepared from (A) :( B):
(C) = 1: 0.01 to 4: 0.1 to 20 (molar ratio), a copolymer having a number average molecular weight of 500 to 400,000 and being copolymerized,
(D) At least one selected from the group consisting of alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates, ammonia, urea, organic amines, acetates, phosphates, nitrates and nitrites. The present invention provides a water-containing lubricant containing a reaction product with a basic compound.

Further, the present invention is secondly selected from the group consisting of (A) α-olefin having 2 to 12 carbon atoms, (B) styrene, vinyl chloride, vinyl acetate, vinyl propionate, acrylonitrile, alkyl vinyl ether and acrylates. At least one vinyl compound and (C) maleic acid or a derivative thereof, which are (A) :( B) :( C)
= 1: 0.01 to 4: 0.1 to 20 (molar ratio), a copolymer having a number average molecular weight of 500 to 400,000 and (D) an alkali metal hydroxide, an alkali metal carbonate or an alkali metal. Reaction product with at least one basic compound selected from the group consisting of hydrogen carbonate, ammonia, urea, organic amines, acetates, phosphates, nitrates and nitrites, and (E) alkylene glycol The present invention provides a water-containing lubricant containing

The component (A) in the copolymer of the present invention has 2 to 2 carbon atoms.
It is 12 α-olefins. Although such an α-olefin may be linear or branched,
Particularly, those having 2 to 8 carbon atoms are preferable. Specifically, ethylene, propylene, n-butylene, isobutylene, n-pentene, isoprene, 2-methyl-1-butene, n-hexene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4 -Methyl-1-pentene, 2-ethyl-1-butene,
Examples thereof include 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethylbutadiene, 2,5-heptadiene, 1,3-octadiene and cyclohexene. Among these, isobutylene is particularly preferable from the viewpoint of easy availability.
The above α-olefins may be used alone or in combination of two or more.

Next, the component (B) in the copolymer in the present invention is a vinyl compound.

The vinyl compound as the component (B) in the copolymer of the present invention includes styrene, vinyl chloride, vinyl acetate,
At least one vinyl compound selected from the group consisting of vinyl propionate, acrylonitrile, alkyl vinyl ethers and acrylic acid esters is used.
These vinyl compounds are compounds that can be copolymerized with maleic acid or its derivatives as the component (C), and specific examples include styrene, vinyl chloride, vinyl acetate, vinyl propionate, acrylonitrile, and methyl. Examples thereof include alkyl vinyl ethers such as vinyl ether, ethyl vinyl ether and propyl vinyl ether, and acrylic acid esters such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate and octyl acrylate. As the component (B), these vinyl compounds may be used alone or in combination of two or more. Styrene is particularly preferable as the vinyl compound.

Further, the component (C) in the copolymer of the present invention is maleic acid derivatives. As the maleic acid derivatives, maleic acid, maleic anhydride, or halogen- or alkyl-substituted derivatives thereof, and esters of these, in which the alkyl group has 1 to 18 carbon atoms, monoalkyl ester or dialkyl ester are preferred. . As the component (C), these maleic acid derivatives can be used alone or in admixture of two or more.
Maleic anhydride is particularly preferred as the maleic acid derivative.

In the ternary copolymer, the composition ratio of each copolymerization component is such that (A) 1 mol of α-olefin having 2 to 12 carbon atoms, 0.01 to 4 mol of (B) vinyl compound and (C) vinyl compound. ) 0.1-20 mol of maleic acid or its derivatives, preferably 0.1-2 mol of component (B) and 0.5-3 mol of component (C) per 1 mol of component (A). If the amount of the component (B) is less than 0.1 mol, the pH of the hydrous lubricant will be too high, while if it exceeds 2 mol, the water solubility of the reaction product will decrease, which is not preferable. Further, if the amount of the component (C) is less than 0.5 mol, the water solubility of the reaction product decreases, while if it exceeds 3 mol, the pH of the hydrous lubricant becomes too high, which is not preferable.

The number average molecular weight of the terpolymer is 500 to 400,000, preferably 5,000 to 200,000. Here, if the number average molecular weight of the terpolymer is less than 500, the thermal stability becomes insufficient, which is not preferable. On the other hand, if it exceeds 400,000, thermal diffusion tends to be uneven, which is not preferable.

The water-containing lubricant of the present invention comprises such a terpolymer,
(D) A reaction product with a basic compound.

Here, as the basic compound, an alkali metal hydroxide,
At least one basic compound selected from the group consisting of alkali metal carbonates, alkali metal hydrogen carbonates, ammonia, urea, organic amines, acetates, phosphates, nitrates and nitrites is used. That is, as the basic compound, specifically, an alkali metal hydroxide such as potassium hydroxide, sodium hydroxide or lithium hydroxide,
Alkali metal carbonates such as potassium carbonate and sodium carbonate, alkali metal hydrogen carbonates such as potassium hydrogen carbonate and sodium hydrogen carbonate, organic amines such as ammonia, urea, methylamine, ethylamine and propylamine, acetates and phosphates , Nitrates and nitrites are used. As the component (D), these basic compounds are used alone or in combination of two or more kinds. Of these, potassium hydroxide, sodium hydroxide, and ammonia are preferable as the basic compound.

The reaction product of the copolymer and the basic compound (D) can be produced, for example, as follows. That is,
First, when isobutylene is used as the component (A), a predetermined amount of each copolymerization component except isobutylene is charged into a reaction vessel, cooled and sufficiently degassed. Then, a predetermined amount of isobutylene is added and the copolymerization reaction is carried out while stirring. At this time, the reaction temperature is not particularly limited,
Usually 30 to 200 ° C, preferably 45 to 150 ° C, the reaction time is 0.
It is set to 5 to 30 hours, preferably 1 to 10 hours. In this copolymerization reaction, a solvent such as acetonitrile, nitromethane, nitroethane, methyl ethyl ketone, acetone, N, N-dimethylformamide, dimethyl sulfoxide, benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, a Catalysts such as butyl butyl hydroperoxide, dicumyl peroxide and azobisisobutyronitrile can be used.

After that, the terpolymer thus obtained is neutralized with a basic compound to obtain a reaction product. At this time, the reaction temperature is preferably set to 20 to 150 ° C. and the reaction time is preferably set to 0.5 to 20 hours.

Further, the above basic compound is used in a proportion of 0.5 to 2 times equivalent, preferably 0.8 to 1.2 times equivalent to maleic acid or its derivatives in the copolymer. If it is less than 0.5 equivalents, the water solubility is insufficient and the pH is too low, while if it exceeds 2 equivalents, the pH becomes too high, which is disadvantageous. In addition, when obtaining this reaction product, water is added to make an alkaline aqueous solution.

Next, the second aspect of the present invention is that the above reaction product is further mixed with alkylene glycol as the component (E). Here, the alkylene glycol preferably has 2 to 6 carbon atoms, and Examples thereof include ethylene glycol, diethylene glycol, triethylene glycol, trimethylene glycol, propylene glycol, dipropylene glycol, hexylene glycol, butylene glycol and the like.

In the second aspect of the present invention, 5 to 80% by weight, preferably 10 to 70% by weight of the above alkylene glycol is added to 95 to 20% by weight, preferably 90 to 30% by weight of the reaction product. If the mixing ratio of the alkylene glycol is less than 5% by weight, the gelation preventing effect by the mixing of the alkylene glycol cannot be said to be sufficient. On the other hand, if the blending ratio of alkylene glycol exceeds 80% by weight, the concentration of the reaction product that improves wear resistance and corrosion resistance becomes low, which is not preferable.

In the present invention, the compound thus obtained is diluted with water to 500 times or less, preferably 200 times or less before use.

In the present invention, if necessary, rust preventives such as alkanolamine and cyclohexylamine; oily agents such as fatty acids; defoaming agents and the like can be appropriately added.

〔The invention's effect〕

The water-containing lubricant of the present invention has excellent wear resistance.
Moreover, the water-containing lubricant of the present invention has a high pH of 9 to 11 and is excellent in corrosion resistance.

Further, the second hydrous lubricant of the present invention has an excellent gelation-preventing effect, and does not have a problem of being attached to a pipe wall or other lubricated portions.

Therefore, the present invention can be effectively used as a hydraulic fluid, a metal working fluid for rolling / drawing, a heat treatment fluid, and the like, particularly as a hydraulic fluid. This is because the corrosion resistance and wear resistance are maintained even after long-term cyclic use.

〔Example〕

Next, the present invention will be described with reference to examples, but the present invention is not limited to these examples without exceeding the scope of the present invention.

Production Examples 1 to 2 (Production of Terpolymer) An autoclave having an internal volume of 1 l was charged with the indicated components except for isobutylene in the indicated amounts, cooled to -10 ° C, and the inside of the container was sufficiently deaerated. Then, the indicated amount of isobutylene and 460 cc of acetonitrile as a solvent and 0.6 g of benzoyl peroxide as a catalyst were added, and 110% while stirring at 400 rpm.
The copolymerization reaction was carried out at 0 ° C. for 2 hours, and then the product was put into water to obtain a copolymer. The number average molecular weight, acid value (mgKOH / g), styrene content and maleic acid content of the obtained copolymer are shown in Table 1 in molar ratio.

Example 1 240 g of isobutylene / styrene / maleic anhydride copolymer obtained in Production Example 1, 120 g of potassium hydroxide and 640 g of water
Were mixed and reacted with stirring at 90 ° C. for 6 hours to obtain a reaction product I.

This reaction product I was diluted with water in the proportions shown in Table 2 to obtain a water-containing circulating agent, and various performance evaluations were carried out by the following methods. The results are shown in Table 2.

(1) Corrosion test According to “metal corrosion test method” shown in 5.4.8 of JIS K2241 (2) Shell four-ball wear resistance test In accordance with ASTM D-4172, wear scar diameter (mm) is shown.

Conditions: Rotation speed: 1800 rpm Load: 10 kg Time: 30 minutes (3) Moisture evaporation test Approximately 50 g of a sample was sampled in a 200 ml beaker, heated on a hot plate and left for 3 to 8 hours before the sample It was observed whether it solidified.

Example 2 A water-containing lubricant was obtained and various performance evaluations were performed in the same manner as in Example 1 except that propylene glycol was further added to the reaction product I in the ratio shown in Table 2. The results are shown in Table 2.

Example 3 234 g of isobutylene / styrene / maleic anhydride copolymer obtained in Production Example 1, 143 g of potassium hydroxide and 623 g of water
Was reacted at 90 ° C. for 6 hours with stirring to obtain a reaction product II.

Propylene glycol was added to this reaction product II and further diluted with water to obtain a hydrous lubricant, and various performance evaluations were performed in the same manner as in Example 1 below. The results are shown in Table 2.

Example 4 In Example 1, the copolymer obtained in Production Example 2 was used in place of the copolymer obtained in Production Example 1 to produce a reaction product II.
Got I. A water-containing lubricant was obtained in the same manner as in Example 1 except that propylene glycol was added to this reaction product III in the ratio shown in Table 2, and various performance evaluations were performed. The results are shown in Table 2.

Comparative Example 1 The same procedure as in Example 3 was repeated except that an ethylene oxide-propylene oxide copolymer (weight average molecular weight 27,000) was used instead of the isobutylene / styrene / maleic anhydride copolymer. . The results are shown in Table 2.

Example 5 The cooling performance was evaluated according to JIS K 2526 using a liquid obtained by diluting an equal amount (weight) mixture of the reaction product II and propylene glycol obtained in Example 3 with water twice. The results are shown in FIG. 1 together with the cooling performance when water was used as a control.

The following can be seen from FIG. That is, when rapidly cooled in the temperature range of 300 to 250 ° C., quench cracking is likely to occur due to uneven burning caused by martensitic transformation, but the product of the present invention tends to have a lower temperature in the above temperature range than water (cooling). It can be seen that since the speed) is small, there is little unevenness in firing and quench cracking does not easily occur.

[Brief description of drawings]

FIG. 1 is a graph showing the results of a cooling test conducted according to JIS K 2526.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location (C10M 109/02 107: 28 107: 38 107: 42 103: 06 A 9159-4H D 9159-4H 103: 00 Z 9159-4H 105: 58 105: 24 105: 68) C10N 10:02 20:04 30:06 30:12 40:08 8217-4H 40:20 A 8217-4H 40:24 Z 8217-4H

Claims (4)

[Claims] 1. An (A) α-olefin having 2 to 12 carbon atoms,
(B) at least one vinyl-based compound selected from the group consisting of styrene, vinyl chloride, vinyl acetate, vinyl propionate, acrylonitrile, alkyl vinyl ethers and acrylates, and (C) maleic acid or a derivative thereof, (A) :( B) :( C) = 1: 0.01
A copolymer having a number average molecular weight of 500 to 400,000, which is copolymerized at a ratio of about 4: 0.1 to 20 (molar ratio), and (D) an alkali metal hydroxide, an alkali metal carbonate, an alkali metal hydrogen carbonate, A hydrous lubricant containing a reaction product with at least one basic compound selected from the group consisting of ammonia, urea, organic amines, acetates, phosphates, nitrates and nitrites. 2. The hydrous lubricant according to claim 1, wherein the basic compound is used in a proportion of 0.5 to 2 equivalents relative to maleic acid or its derivatives in the copolymer. 3. (A) an α-olefin having 2 to 12 carbon atoms,
(B) at least one vinyl-based compound selected from the group consisting of styrene, vinyl chloride, vinyl acetate, vinyl propionate, acrylonitrile, alkyl vinyl ethers and acrylates, and (C) maleic acid or a derivative thereof, (A) :( B) :( C) = 1: 0.01
A copolymer having a number average molecular weight of 500 to 400,000, which is copolymerized at a ratio of about 4: 0.1 to 20 (molar ratio), and (D) an alkali metal hydroxide, an alkali metal carbonate, an alkali metal hydrogen carbonate, Water containing a reaction product with at least one basic compound selected from the group consisting of ammonia, urea, organic amines, acetates, phosphates, nitrates and nitrites, and (E) alkylene glycol lubricant. 4. The hydrous lubricant according to claim 3, wherein the basic compound is used in a proportion of 0.5 to 2 equivalents relative to maleic acid or its derivatives in the copolymer.