JP2608537B2 - Thickened high water content hydraulic fluid - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a highly water-containing hydraulic fluid used for a hydraulic device at a place where a fire is used to prevent construction fires. More specifically, the present invention relates to a thickened, highly hydrated hydraulic fluid that exhibits a large thickening effect with a small amount of a thickener, has excellent shear stability, and has a high cloud point.

(Conventional technology) A hydrous hydraulic fluid is used in a hydraulic device at a place where a fire is used to prevent fire in construction. The most frequently used hydrous hydraulic fluid is a water-glycol hydraulic fluid containing about 30 to 50% each of water and glycol.
However, on the other hand, from the viewpoint of higher fire resistance, resource saving, and cost reduction, much research has been conducted on a highly water-containing hydraulic fluid in which the water content is greatly increased.

Increasing the water content, on the other hand, has the above-mentioned advantages, but often adversely affects the performance required as a working fluid. Specifically, the viscosity of the conventional high water content hydraulic fluid is almost the same as that of water with some exceptions, and is about 1 cSt. As a result, the leakage of the hydraulic fluid is extremely large, and the efficiency of the hydraulic pump is significantly reduced, which causes an increase in running cost and a deterioration of the working environment in the construction. Further, the lubricating property is remarkably inferior to other hydraulic fluids, and is limited to use at very low pressure.

(Problems to be Solved by the Invention) In order to improve these drawbacks, there is an example of an attempt to increase the viscosity of a highly water-containing hydraulic fluid by adding a water-soluble thickener. Water-soluble thickeners that have been used for low molecular weight materials have a low thickening effect and require a large amount of addition. The viscosity decreases during use. Further, when these thickeners are used in an aqueous solution including those having relatively low molecular weight, the thickener is separated at a high temperature due to the cloud point phenomenon, so that there is a problem in stability at a high temperature.

The problem to be solved by the present invention is to develop a thickened, highly hydrated hydraulic fluid that exhibits a large thickening effect by adding a small amount of a thickener, and is excellent in shear stability and high-temperature stability. is there.

(Means for Solving the Problems) The present inventors have made various studies to improve the above-mentioned disadvantages, and as a result, have found that a polyalkylene having a specific structure in which butylene oxide is added as a hydrophobic group to the terminal of a water-soluble thickener. By solubilizing the oxide-type thickener in water with a fatty acid soap having about 12 or more carbon atoms, a large thickening effect is exhibited despite addition of a small amount of the thickener, and shear stability and high temperature The present inventors have found that a thickened, highly water-containing working fluid having excellent stability can be obtained, and completed the present invention.

That is, the gist of the present invention is to contain 75 to 98% by weight of water, 1 to 15% by weight of a polyalkylene oxide represented by the formula [I], and 1 to 10% by weight of a fatty acid soap having 12 or more carbon atoms, and to contain 5% by weight of glycols. Thickened high water content hydraulic fluid characterized by containing only the following: R (X [｛(C ₂ H ₄ O) _a (C ₃ H ₆ O) _b ｝ (C ₄ H ₈ O) _c H] _d )
_e [I] (where R is a residue of a polyhydric alcohol, polyhydric phenol or polyamine having 2 to 26 carbon atoms, X is an oxygen atom or a nitrogen atom, a + b is 10 to 600, and b / a is 0 to 7 / 3, c is 1-7
0, d is 1 or 2, e is 2 to 8, and the sequence of the unit in ｛｝ is arbitrary, including random and block, but the unit of C ₄ H ₈ O is a block at the end of the chain. Exist in the form. ).

 Hereinafter, the present invention will be described in detail.

The polyalkylene oxide used in the present invention is represented by the following formula [I].

R (X [｛(C ₂ H ₄ O) _a (C ₃ H ₆ O) _b ｝ (C ₄ H ₈ O) _c H] _d )
_e [I] (where R is a residue of a polyhydric alcohol, polyhydric phenol or polyamine having 2 to 26 carbon atoms, X is an oxygen atom or a nitrogen atom, a + b is 10 to 600, and b / a is 0 to 7 / 3, c is 1-7
0, d is 1 or 2, and e is 2-8. In the formula (I), as the polyhydric alcohol having 2 to 26 carbon atoms, polyhydric phenol or polyamine having R as a residue, ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, octylene glycol, glycerin, Trimethylolpropane, erythritol, pentaerythritol, sorbitol, glucose, sucrose, ethyldiethanolamine, butyldiethanolamine, triethanolamine, tripropanolamine, N, N'-di-naphthyl-p-phenylenediamine, 4,4'-di -Aminodiphenylmethane, ethylenediamine, diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, pentaethylenehexamine, bisphenol A, 4,4'-butylidenebis (6-tertiary Butyl-3-methylphenol), 4,4'-thiobis (6-tert-butyl-3
-Methylphenol), catechol, resorcinol and the like. E is an integer of 2 to 8 corresponding to the valence of R.

The polyalkylene oxide of the formula (I) is prepared by polyaddition of ethylene oxide and propylene oxide in a random or block manner with polyhydric alcohol, polyhydric phenol or polyamine having R as a starting material. It is obtained by obtaining an ethyleneoxypropylene compound and then subjecting butylene oxide to addition polymerization at the terminal of the polymer.

[I] In the polyalkylene oxide of the formula, a + b
In other words, the total added mole number of ethylene oxide and propylene oxide is limited to 10 to 600, because if the added mole number is too small, the molecular weight becomes low, it becomes completely water-soluble and no thickening effect is exhibited, and if it is too large, the shear stability becomes too high. Is to be reduced.

The ratio of b / a is limited to 0 to 7/3 because if the ratio is too large, the hydrophobicity becomes too strong, and solubilization in water becomes difficult.

The value of d, that is, the number of moles of butylene oxide added is 1
The reason why the value is limited to ~ 70 is that if the value is too large, the hydrophobicity becomes too strong, and solubilization in water becomes difficult.

The ethylene oxide group and the propylene oxide group are added in random or block form, and the butylene oxide group is added only at the terminal. The terminal butylene oxide group reduces the solubility of the thickener of the formula [I] in water, but has the effect of greatly improving the viscosity when solubilized. In this sense, the alkylene oxide group added to the terminal is not limited to a butylene oxide group, but it is difficult to produce an alkylene oxide group having 5 or more carbon atoms.

The compounding amount of the polyalkylene oxide is about 1 to 15% by weight, preferably about 3 to 12% by weight. If the amount is too small, the thickening effect will not appear, and if it is too large, the significance of high water content will be lost and the cost will be disadvantageous.

The fatty acid soap contained in the highly water-containing working fluid of the present invention is a soap of a fatty acid having about 12 or more, preferably about 12 or more and about 36 or less and an alkali metal or an amine, about 1 to about 10 wt.
%, Preferably about 3 to about 8 wt%. The addition of the fatty acid soap solubilizes the thickener in water and improves the viscosity. Therefore, if the amount is too small, the thickener will not be solubilized, and if the amount is too large, the effect will not be so significant. Fatty acids having about 12 or more carbon atoms have a remarkable effect of increasing the cloud point and improve the stability at high temperatures. However, when the chain length of the fatty acid is too long, the solubility of the fatty acid soap in water is reduced. Specifically, lauric acid,
Preference is given to potassium or sodium salts of myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, erucic acid or monoethanolamine salts.

That is, in the present invention, the addition polymerization of a butylene oxide group at the end of the addition polymer of an ethylene oxide group and a propylene oxide group results in a decrease in the solubility of this polyalkylene oxide in water. However, solubilization was realized by using the above fatty acid soap in combination. As a result, not only a large thickening effect was obtained by adding a small amount of the polyalkylene oxide, but also the effect of increasing the cloud point was obtained by using a specific fatty acid soap.

Other additives that can be included in the highly water-containing working fluid of the present invention include hydroxides of alkali metals and amines as pH adjusters, and ethylene glycol, diethylene glycol, triethylene glycol, and propylene as pour point depressants. Glycol, dipropylene glycol,
Sulfur compounds as extreme pressure agents, such as hexylene glycol,
Examples include phosphorus compounds, metal salts of aminocarboxylic acids such as ethylenediaminetetraacetic acid as sequestering agents, and metal salts and amine salts such as mercaptobenzothiazole and triazole as corrosion inhibitors.

The amount of these additives is 5% by weight or less, preferably 3% by weight or less.

(Effects of the Invention) As described in detail above, according to the highly water-containing working fluid of the present invention, since a specific polyalkylene oxide and a specific fatty acid soap are used in combination, a polyalkylene oxide that does not dissolve alone can be solubilized, In addition, it exhibits a large thickening effect for a small amount of the compound, and is excellent in shear stability.
In addition, since the cloud point is greatly increased by blending the above fatty acid soap at a specific ratio, the high temperature stability is excellent, and the volume efficiency is not reduced even in the operation of the pump under a relatively high pressure, and the anti-friction ability is also excellent. .

Furthermore, it can be manufactured at a much lower cost than water-glycol hydraulic oil.

(Examples) Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.

Production examples of polyalkylene oxide used in Examples and Comparative Examples are shown below.

Production Example 1 Production of polyalkylene oxide represented by formula [I] (R
Is a polyhydric alcohol) 310 g (5 mol) of ethylene glycol, 110 g of potassium hydroxide as a catalyst, ethylene oxide in a nitrogen gas atmosphere
33 kg (750 mol) and 14.5 kg (250 mol) of propylene oxide were polymerized at 100 to 140 ° C. under a pressure of 0.5 to 5 kg / cm ² to obtain 47.5 kg of polyoxyethyleneoxypropylene glycol.

Next, 47.5 kg of the above product (polyoxyethylene oxypropylene glycol) and 4.32 kg (60 mol) of butylene oxide were added together with 120 g of a potassium hydroxide catalyst under a nitrogen gas atmosphere at 80 to 120 ° C. under a pressure of 0.5 to ⁵ kg / cm ² . To obtain polyoxyethyleneoxypropyleneoxybutylene glycol having a butylene oxide group added only to the terminal.
After neutralizing potassium hydroxide in this crude reaction product with aqueous hydrochloric acid
The solution was dehydrated at 80 to 120 ° C. under a reduced pressure of 50 mmHg or less for 2 hours, and the precipitated salt was separated by filtration to obtain 51 kg of a purified reaction product. The obtained polyoxyethylene oxypropylene oxybutylene glycol was of the following formula.

C ₂ H ₄ [O ｛C ₂ H ₄ O) ₇₅ (C ₃ H ₆ O) ₂₅ ｝ (C ₄ H ₈ O) ₆ H] ₂ Examples 1-4, Comparative Examples 1-5 Examples 1-4 , Compositions of Comparative Examples 1 to 5, kinematic viscosity, cloud point,
The shear stability is shown in Tables 1 and 2.

Each of the high water-containing hydraulic fluids shown in Examples 1, 2, 3, and 4 was thickened to a kinematic viscosity equivalent to that of a water-glycol hydraulic oil with 5% by weight of a thickening agent, and the stage stability and the cloud point were increased. Indicates a value that is practically acceptable.

Examples 5 to 7 and Comparative Examples 6 to 21 Cloud points were measured using various substances as solubilizers in the following formulation.

<Formulation> C ₂ H ₄ [O ｛(C ₂ H ₄ O) ₁₅₀ (C ₃ H ₆ O) ₄₀ ｝ (C ₄ H ₈ O) ₁₂ H] ₂ 5 wt% Solubilizer 5 wt% Water 90 wt% Various possible Table 3 shows the solubilizers and the results.

Next, a production example in which R is a polyamine or polyhydric phenol residue in the formula [I] will be described.

Production Example 2 300 g (5 mol) of ethylenediamine, 50 g of potassium hydroxide as a catalyst, and 52 g of ethylene oxide in a nitrogen gas atmosphere.
8 kg (1200 mol) and 17.4 kg (300 mol) of propylene oxide are polymerized at 100 to 140 ° C. under a pressure of 0.5 to ⁵ kg / cm ² to obtain polyoxyethylene oxypropylene ethylene diamine 7
0.2 kg was obtained.

Next, 70.2 kg of the above product (polyoxyethyleneoxypropylene ethylenediamine) and 5.76 kg of butylene oxide
(80 mol) was polymerized with 150 g of potassium hydroxide catalyst in a nitrogen gas atmosphere at 80 to 120 ° C. under a pressure of 0.5 to ⁵ kg / cm ² , and polyoxyethyleneoxypropyleneoxybutylene having a butylene oxide group added only to the terminal. Ethylenediamine was obtained. This crude reaction product was purified in the same manner as in Production Example 1 to obtain 75.9 kg of a purified reaction product.

The obtained polyoxyethyleneoxypropyleneoxybutyleneethylenediamine had the following formula.

C ₂ H ₄ (N [｛(C ₂ H ₄ O) ₆₀ (C ₃ H ₆ O) ₁₅ ｝ (C ₄ H ₈ O) ₄ H] ₂ ) ₂ Production Example 3 (CH ₃ ) ₂ C (C ₆ Bisphenol A represented by H ₄ OH) ₂
1140 g (5 mol), potassium hydroxide 150 g as catalyst, ethylene oxide 44 kg (1000 mol) under nitrogen gas atmosphere,
17.4 kg (300 mol) of propylene oxide at 100-140 ° C,
Polymerization was performed under a pressure of 0.5 to ⁵ kg / cm ² to obtain 61.4 kg of polyoxyethyleneoxypropylene bisphenol A.

Next, 61.4 kg of the above product (polyoxyethylene oxypropylene bisphenol) and 5.76 kg of butylene oxide
(80 mol) was polymerized with 150 g of potassium hydroxide catalyst in a nitrogen gas atmosphere at 80 to 120 ° C. under a pressure of 0.5 to ⁵ kg / cm ² , and polyoxyethyleneoxypropyleneoxybutylene having a butylene oxide group added only to the terminal. Bisphenol A was obtained. This crude reaction product was purified in the same manner as in Production Example 1 to obtain 67 kg of a purified reaction product.

The obtained polyoxyethyleneoxypropyleneoxybutylene bisphenol A was of the following formula.

(CH ₃ ) ₂ C (C ₆ H ₄ ) ₂ [｛O (C ₂ H ₄ O) ₁₀₀ (C ₃ H ₆ O) ₃₀ } (C ₄ H ₈ O) ₈ H]
₂ Examples 8 and 9 Table 4 shows the composition, kinematic viscosity, cloud point, and shear stability of an example of the working fluid using the products obtained in Production Examples 2 and 3.

(High-pressure pump test) Highly water-containing hydraulic fluid of Example 1 and Comparative Example 1 and commercially available O / W
A vane pump test was performed on the highly hydrous working fluid under the following conditions.

Pump Vane pump (rated pressure 175kgf / cm ² ) Motor speed 1200rpm Oil temperature 40 ℃ Test time 100hr Evaluation item Volumetric efficiency (%) Wear (mg) (Total weight loss of cam ring, vane and bushing) Table 5 Shown in

The highly water-containing hydraulic fluid of Example 1 had a volume efficiency of 85.3% in a test at a pressure of 140 kgf / cm ² , and the total wear after 100 hours was 75 mg. Occasionally an abnormal sound was generated, and the test at 140 kgf / cm ² could not be performed. In addition, 35kg which was done for reference
In the test at f / cm ² , the O / W emulsion type high water content hydraulic fluid showed a volumetric efficiency of 60.5% and a total wear of 1070 mg.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical indication location C10N 40:08 (72) Inventor Yasuo Iwamiya 1-8-27 Hanada, Koshigaya-shi, Saitama (56) Reference Document JP-A-2-120398 (JP, A) JP-A-57-105492 (JP, A) JP-A-58-96698 (JP, A) JP-A-58-63776 (JP, A) 29898 (JP, A)

Claims (1)

(57) [Claims] (1) It contains 75 to 98% by weight of water, 1 to 15% by weight of a polyalkylene oxide represented by the formula [I], and 1 to 10% by weight of a fatty acid soap having 12 or more carbon atoms, and contains 5% by weight of a glycol.
% Thickened hydraulic fluid R (X [｛(C ₂ H ₄ O) _a (C ₃ H ₆ O) _b ｝ (C ₄ H ₈ O) _c H] _d )
_c [I] (where R is a residue of a polyhydric alcohol, polyhydric phenol, or polyamine having 2 to 26 carbon atoms, X is an oxygen atom or a nitrogen atom, a + b is 10 to 600, and b / a is 0 to 7 / 3, c is 1-7
0, d is 1 or 2, e is 2 to 8, and the sequence of the unit in ｛｝ is arbitrary, including random and block, but the unit of C ₄ H ₈ O is a block at the end of the chain. Exist in the form. ).