KR20070111762A - Fire resistant hydraulic fluids - Google Patents

Abstract

A hydraulic fluid composition is provided to ensure a controllable viscosity, to accomplish minimization of a drop in viscosity caused by shear, and to obtain excellent properties including a flash point, flow point, viscosity index, oxidation stability, wear resistance and load resistance. A hydraulic fluid composition comprises a base material, such as polyol ester, defoaming agent, thickening agent and flame retardant, wherein the base material is a polyol ester obtained by performing partial polymerization of a C6-C24 saturated or unsaturated fatty acid represented by any one of the following formulae 1-4 with mixed alcohols under nitrogen atmosphere at 130-270 deg.C for 10-30 hours. In formulae 1 and 2, R represents independently a C2-C11 saturated or unsaturated alkyl group, X1 is a bond between two molecules, and X2 is a bond among three molecules. In formula 3, n is an integer of 1-12. In formula 4, R1 and R2 are the same or different, and each represents a C1-C4 alkyl or (CH2)nOHn, wherein n represents independently an integer of 1-2.

Description

Fire resistant hydraulic fluids

The present invention relates to a hydraulic hydraulic oil composition, and more particularly, to the synthesis of a composite alcohol and a polyol ester-based hydraulic oil base containing the base fatty acid, and a hydraulic hydraulic oil using the same.

Synthetic lubricating oil was developed to improve the properties of petroleum-based lubricants, but the conventional synthetic lubricating oil used a viscosity index improver to maintain the appropriate viscosity of the polyol esters used as a base, and thus, due to the shearing of the working oil Viscosity drop phenomenon

The present invention relates to a new, higher-quality hydraulic fluid that solves the above-mentioned problems, and uses a polyol ester obtained by synthesizing a mixed fatty acid and a mixed alcohol under a catalyst-free atmosphere. This polyol ester has a very high viscosity index of its own, and the flame retardancy also has the side effect of being higher than the conventional polyol ester hydraulic fluid.

The polyol ester base used in the present invention is synthesized using a saturated or unsaturated fatty acid having 6 to 24 carbon atoms and mixed alcohol. Alkyl groups of fatty acids are applicable either straight or branched and the choice should take into account the lubricity of the composition or other physical properties.

In formula (1), R is the same or different saturated or unsaturated alkyl group having 2 to 10 carbon atoms.

In general, carbon has a molecular structure having four side branches, but a polymeric acid having a crosslinking role as a breakage of the -bond of an unsaturated group may be obtained.

In formula (3), n is a C1-C12 saturated or unsaturated alkyl group.

R1 and R2 are the same or different alkyl groups having 1 to 4 carbon atoms or (CH2) nOH, n is an integer of 1 to 2;

The present invention is obtained by mixing an appropriate amount of an antioxidant, an anti-wear additive, a thickener and the like with a polyol ester synthesized under a catalyst.

Specifically, the antioxidant has the best effect of the phenylnaphthylamine (formula 5), but may also use an antioxidant such as a metal salt of phenyl, phosphate ester and phosphate ester (eg, Zn-DTP).

The addition amount is 0.2-11.0 weight part, Preferably it is 2.0-4.0 weight part.

In general, less than 1.0 parts by weight, the effect is small, if more than 8.0 parts by weight can be expected the effect of the anti-oxidation, there may be a problem such as discoloration of the emulsion and degradation of the flame retardant effect.

R is hydrogen or a C1-C10 alkyl group here. As an antiwear additive, the effect of an aryl phosphate type | system | group (five formulas below) is the best, and the metal salt of a phosphate ester, the amine salt of a phosphate ester, and the additive of a sulfide may be used together. The addition amount is 0.2-8.0 weight part, Preferably it is 0.5-3.0 weight part.

In this invention, 0.01-1.0 weight part of corrosion inhibitors, an antifoamer, etc. can also be added as needed.

The above-mentioned additives are very necessary in the lubricating oil composition, but when used in excess of the appropriate range, the flame retardant effect may be reduced, the viscosity decrease due to shearing, the generation of tailings, and the discoloration of the emulsion may be appropriately combined with the base oil and the additive. Should be considered.

Example 1 Selection of Synthesis Conditions

In selecting a reaction temperature for obtaining a polyol ester base used in the present invention, first, experiments were carried out by varying the temperature range from 130 ° C to 270 ° C.

At this time, when the synthesis temperature is 150 ℃ or less, the reaction rate is very slow and the amount of Carrier gas is injected, whereas the acid value is difficult to reach the desired target value.

In addition, the reaction rate was higher than 250 ℃, but it was confirmed that the thermal oxidation and the polyol and low molecular weight fatty acid evaporated serious effects on the ester base.

The results are shown in Table-1.

TABLE 1

Example 2 Selection of Fatty Acid

Fatty acid used in the present invention was used that can be obtained in the general market, but for the stable properties and performance of the invention is used as having the following physical properties.

1) Oleic acid

Appearance: Below 2.0 (ASTM Color)

Average molecular weight: 250 or more

Purity: Fatty acid with 18 or more carbon atoms

Acid value: 170 (mg KOH / g) or more

2) Dimer acid

Appearance: Below 4.0 (ASTM Color)

Average molecular weight: over 450

Purity: Fatty acid content of 36% or more

Acid value: over 160 (mg KOH / g)

3) Trimer Mount

Appearance: Below 7.0 (ASTM Color)

Average molecular weight: over 600

Purity: More than 40% fatty acid with 54 carbon atoms

Acid value: over 160 (mg KOH / g)

4) dibasic acid

Appearance: White to light brown solid

Purity: The content of dibasic acid is over 80%

5) other fatty acids

Purity: Fatty acid content over 80%

Example 3: Preparation of Base

1) Add 16.0 parts of neopentyl glycol to 84.0 parts by weight of mixed fatty acid of oleic acid and dimer acid, and react for 5 to 20 hours at 160 ℃ ~ 240 ℃ under nitrogen atmosphere (500cc per minute).

When the acid value is 2.5 or less, the reaction is terminated and referred to as an ester of neopentyl glycol (hereinafter referred to as 1-X).

X is a dimer acid content of 0 ~ 10 parts by weight) was obtained (yield 95%). The properties of this ester are as follows.

Appearance: pale yellow transparent liquid

Acid value: Below 3.0

Specific gravity: 0.920 ～ 0.950

Flow point: Below -20.0 ℃

Kinematic viscosity: 24 to 48 (cSt, 40 ℃: Viscosity rises by about 2 cSt for every 1 part by weight of dimer acid)

2) Add 16.0 parts of neopentyl glycol to 84.0 parts by weight of mixed fatty acid of oleic acid and trimer acid and react for 5 to 20 hours at 160 ℃ ~ 240 ℃ under nitrogen atmosphere (500cc per minute).

When the acid value is 2.5 or less, the reaction is terminated to refer to an ester of neofetyl glycol (hereinafter referred to as 2-X).

X is a part by weight of 0 to 10 by weight of the trimer acid.) (Yield 95%)

The properties of this ester are as follows.

Appearance: pale yellow transparent liquid

Acid value: Below 3.0

Specific gravity: 0.920 ～ 0.950

Flow point: Below -20.0 ℃

Kinematic viscosity: 24 ~ 68 (cSt, 40 ℃: Viscosity rises about 4.5cSt for every 1 part by weight of trimer acid)

3) Add 16.0 parts of neopentylglycol to 84.0 parts of mixed fatty acid of oleic acid and dibasic acid and react for 5 to 20 hours at 160 ℃ ~ 240 ℃ under nitrogen atmosphere (500cc per minute).

When the acid value is 2.5 or less, the reaction is terminated to refer to an ester of neopentyl glycol (hereinafter referred to as 3-X).

X is a dibasic acid content of 0 to 10 parts by weight) was obtained (yield 95%).

The properties of this ester are as follows.

Appearance: pale yellow transparent liquid

Acid value: Below 3.0

Specific gravity: 0.920 ～ 0.950

Floating point: -25.0 or less

Kinematic viscosity: 24 ~ 56 (cSt, 40 ℃: Viscosity rises about 3cSt each time 1 part by weight of dibasic acid is added)

4) Add 15.0 parts by weight of trimethylolpropane to 85.0 parts by weight of mixed fatty acid of oleic acid and dimer acid, and react for 5 to 20 hours at 160 ° C to 240 ° C under nitrogen atmosphere (500cc per minute).

When the acid value is 2.5 or less, the reaction is terminated to give an ester of trimethylolpropane (hereinafter referred to as 4-X).

X is a dimer acid content of 0 ~ 10 parts by weight) was obtained (yield 95%).

The properties of this ester are as follows.

Appearance: pale yellow transparent liquid

Acid value: Below 3.0

Specific gravity: 0.920 ～ 0.950

Flow point: Below -20.0 ℃

Kinematic viscosity: 45 to 88 (cSt, 40 ℃: Viscosity rises about 4cSt for every 1 part by weight of dimer acid)

5) Add 15.0 parts by weight of trimetalol propane to 85.0 parts by weight of mixed fatty acid of oleic acid and trimeric acid and react for 5 to 20 hours at 160 ° C to 240 ° C under nitrogen atmosphere (500cc per minute).

When the acid value is 2.5 or less, the reaction is terminated to refer to an ester of trimethylolpropane (hereinafter referred to as 5-X).

X is a dimer acid content of 0 ~ 10 parts by weight) was obtained (yield 95%).

The properties of this ester are as follows.

Appearance: pale yellow transparent liquid

Acid value: Below 3.0

Specific gravity: 0.920 ～ 0.950

Flow point: Below -20.0 ℃

Kinematic viscosity: 45 to 96 (cSt, 40 ° C: Viscosity rises by approximately 4.5 cSt for each additional 1 weight part of trimer acid)

6) Add 15.0 parts by weight of trimethylolpropane to 85.0 parts by weight of mixed fatty acid of oleic acid and dibasic acid, and react for 5 to 20 hours at 160 ° C to 240 ° C under nitrogen atmosphere (500cc per minute).

When the acid value is 2.5 or less, the reaction is terminated to refer to an ester of trimethylolpropane (hereinafter referred to as 6-X).

X is a dibasic acid content of 0 to 10 parts by weight) was obtained (yield 95%).

The properties of this ester are as follows.

Appearance: pale yellow transparent liquid

Acid value: Below 3.0

Specific gravity: 0.920 ～ 0.950

Flow point: Below -20.0 ℃

Kinematic viscosity: 45 ~ 96 (cSt, 40 ℃: Viscosity rises about 4.5cSt with every addition of 1 part by weight of dibasic acid)

7) Add 12.0 parts by weight of pentaerythritol to 88.0 parts by weight of mixed fatty acid of oleic acid and dimer acid, and react for 5 to 20 hours at 160 ℃ ~ 240 ℃ under nitrogen atmosphere (500cc per minute).

When the acid value is 2.5 or less, the reaction is terminated to refer to an ester of pentaerythritol (hereinafter referred to as 7-X).

X is a dimer acid content of 0 ~ 10 parts by weight) was obtained (yield 95%).

The properties of this ester are as follows.

Appearance: pale yellow transparent liquid

Acid value: Below 3.0

Specific gravity: 0.920 ～ 0.950

Flow point: Below -20.0 ℃

Kinematic viscosity: 65 to 125 (cSt, 40 ℃: Viscosity rises about 5cSt for every 1 part by weight of dimer acid)

8) Add 12.0 parts by weight of pentaerythritol to 88.0 parts by weight of mixed fatty acid of oleic acid and trimeric acid, and react for 5 to 20 hours at 160 ℃ to 240 ℃ under nitrogen atmosphere (500cc per minute).

When the acid value is 2.5 or less, the reaction is terminated to refer to an ester of pentaerythritol (hereinafter referred to as 8-X).

X is a part by weight of 0 to 10 parts by weight of the trimer acid.) (Yield 95%).

The properties of this ester are as follows.

Appearance: pale yellow transparent liquid

Acid value: Below 3.0

Specific gravity: 0.920 ～ 0.950

Flow point: Below -20.0 ℃

Kinematic viscosity: 65 ~ 195

9) Add 12.0 parts by weight of pentaerythritol to 88.0 parts by weight of mixed fatty acid of oleic acid and dibasic acid, and react for 5 to 20 hours at 160 ℃ ~ 240 ℃ under nitrogen atmosphere (500cc per minute).

When the acid value is 2.5 or less, the reaction is terminated to refer to an ester of pentaerythritol (hereinafter referred to as 9-X).

X is a dibasic acid content of 0 to 10 parts by weight) was obtained (yield 95%). The properties of this ester are as follows.

Appearance: pale yellow transparent liquid

Acid value: Below 3.0

Specific gravity: 0.920 ～ 0.950

Flow point: Below -20.0 ℃

Kinematic viscosity: 65 to 136 (cSt, 40 ° C: Viscosity rises by about 6 cSt for every 1 part of dibasic acid)

10) Add 24.0 parts of neopentylglycol to 76.0 parts by weight of mixed fatty acid of caprylic acid and dimer acid and react for 5 to 20 hours at 160 ° C to 240 ° C under nitrogen atmosphere (500cc per minute).

When the acid value is 2.5 or less, the reaction is terminated and referred to as neopentyl glycol ester (hereinafter referred to as 10-X).

X is a dimer acid content of 0 ~ 10 parts by weight) was obtained (yield 95%). The properties of this ester are as follows.

Appearance: pale yellow transparent liquid

Acid value: Below 3.0

Specific gravity: 0.910 ～ 0.950

Flow point: Below -20.0 ℃

Kinematic Viscosity: 15 to 35

11) Add 24.0 parts of neopentylglycol to 76.0 parts by weight of mixed fatty acid of caprylic acid and dibasic acid, and react for 5 to 20 hours at 160 ° C to 240 ° C under nitrogen atmosphere (500cc per minute).

When the acid value is 2.5 or less, the reaction is terminated to refer to an ester of neopentyl glycol (hereinafter referred to as base 11-X).

X is a dibasic acid content of 0 to 10 parts by weight) was obtained (yield 95%).

The properties of this ester are as follows.

Appearance: pale yellow transparent liquid

Acid value: Below 3.0

Specific gravity: 0.910 ～ 0.950

Flow point: Below -20.0 ℃

Kinematic Viscosity: 15 to 45

12) Add 21.0 parts by weight of trimethylolpropane to 79.0 parts by weight of mixed fatty acid of caprylic acid and dimer acid and react for 5 to 20 hours at 160 ° C to 240 ° C under nitrogen atmosphere (500cc per minute).

When the acid value is 2.5 or less, the reaction is terminated to refer to an ester of trimethylolpropane (hereinafter referred to as 12-X).

X is a dimer acid content of 0 ~ 10 parts by weight) was obtained (yield 95%).

The properties of this ester are as follows.

Appearance: pale yellow transparent liquid

Acid value: Below 3.0

Specific gravity: 0.910 ～ 0.950

Flow point: Below -20.0 ℃

Kinematic Viscosity: 20 ~ 45

13) Add 21.0 parts by weight of trimethylolpropane to 79.0 parts by weight of mixed fatty acid of caprylic acid and dibasic acid and react for 5 to 20 hours at 160 ° C to 240 ° C under nitrogen atmosphere (500cc per minute).

When the acid value is 2.5 or less, the reaction is terminated to refer to an ester of trimethylolpropane (hereinafter referred to as 13-X).

X is a dibasic acid content of 0 to 10 parts by weight) was obtained (yield 95%).

The properties of this ester are as follows.

Appearance: pale yellow transparent liquid

Acid value: Below 3.0

Specific gravity: 0.910 ～ 0.950

Flow point: Below -20.0 ℃

Kinematic viscosity: 20 ~ 45 (cSt, 40 ℃: Viscosity rises about 2cSt each time adding 1 part by weight of dibasic acid

14) Add 16.0 parts by weight of pentaerythritol to 84.0 parts by weight of the mixed fatty acid of caprylic acid and dimer acid and react for 5 to 20 hours at 160 ° C to 240 ° C under nitrogen atmosphere (500cc per minute).

When the acid value is 2.5 or less, the reaction is terminated to refer to an ester of pentaerythritol (hereinafter referred to as 14-X).

X is a dimer acid content of 0 ~ 10 parts by weight) was obtained (yield 95%).

The properties of this ester are as follows.

Appearance: pale yellow transparent liquid

Acid value: Below 3.0

Specific gravity: 0.910 ～ 0.950

Flow point: Below -20.0 ℃

Kinematic Viscosity: 33 ~ 65

15) Add 16.0 parts of pentaerythritol to 84.0 parts of mixed fatty acid of caprylic acid and dibasic acid and react for 5 to 20 hours at 160 ℃ ~ 240 ℃ under nitrogen atmosphere (500cc per minute).

When the acid value is 2.5 or less, the reaction is terminated to refer to an ester of pentaerythritol (hereinafter referred to as 15-X).

X is a dibasic acid content of 0 to 10 parts by weight) was obtained (yield 95%). The properties of this ester are as follows.

Appearance: pale yellow transparent liquid

Acid value: Below 3.0

Specific gravity: 0.910 ～ 0.950

Flow point: Below -20.0 ℃

Kinematic viscosity: 33 to 65 (cSt, 40 ℃: Viscosity rises by about 3 cSt for each additional 1 part of dibasic acid)

16) Add 16.0 parts of neopentylglycol to 84.0 parts by weight of the mixed fatty acid of isostearic acid and dimer acid and react for 5 to 20 hours at 160 ℃ ~ 240 ℃ under nitrogen atmosphere (500cc per minute).

When the acid value is 2.5 or less, the reaction is terminated to refer to an ester of neopentyl glycol (hereinafter referred to as 16-X).

X is a dimer acid content of 0 ~ 10 parts by weight) was obtained (yield 95%).

The properties of this ester are as follows.

Appearance: pale yellow transparent liquid

Acid value: Below 3.0

Specific gravity: 0.920 ～ 0.950

Flow point: Below -20.0 ℃

Kinematic Viscosity: 85 ~ 176

17) Add 15.0 parts by weight of trimethylolpropane to 85.0 parts by weight of mixed fatty acid of isostearic acid and dimer acid, and react for 5 to 20 hours at 160 ° C to 240 ° C under nitrogen atmosphere (500cc per minute).

When the acid value is 2.5 or less, the reaction is terminated to refer to an ester of trimethylolpropane (hereinafter referred to as 17-X).

X is a dimer acid content of 0 ~ 10 parts by weight) was obtained (yield 95%).

The properties of this ester are as follows.

Appearance: pale yellow transparent liquid

Acid value: Below 3.0

Specific gravity: 0.920 ～ 0.950

Flow point: Below -20.0 ℃

Kinematic Viscosity: 102 ~ 216

18) Add 12.0 parts by weight of pentaerythritol to 82.0 parts by weight of mixed fatty acid of isostearic acid and dimer acid, and react for 5 to 20 hours at 160 ℃ ~ 240 ℃ under nitrogen atmosphere (500cc per minute).

When the acid value is 2.5 or less, the reaction is terminated to refer to an ester of pentaerythritol (hereinafter referred to as 18-X).

X is a dimer acid content of 0 ~ 10 parts by weight) was obtained (yield 95%).

The properties of this ester are as follows.

Appearance: pale yellow transparent liquid

Acid value: Below 3.0

Specific gravity: 0.920 ～ 0.950

Flow point: Below -20.0 ℃

Kinematic viscosity: 136 to 276 (cSt, 40 ° C: viscosity increases about 12 cSt for every 1 part by weight of dimer acid) When the catalyst is used in the synthesis of the ester described above, the amount of catalyst to be added is 0.01 to 1.0 parts by weight, preferably Is 0.02 to 0.3 parts by weight.

At this time, the weight part of the catalyst is subtracted from the weight part of the fatty acid.

Normal esters generally have a structure such as the following formula (7), but esters in the present invention partially form the polymer structure of the formula (7) by introducing polymeric acid and dibasic acid.

The amount of the polymer structure produced depends on the amount of the polymeric acid and the dibasic acid. The more the polymer structure is produced, the higher the viscosity of the ester is, and the flame retardancy (flash point, combustion point, etc.) is also improved.

Here, the increase in viscosity is in accordance with Example 3 described above, and the improvement of flame retardancy varies depending on the ester base, but usually has an improvement effect of about 2 to 5 ° C. for each addition of 1 part by weight of polymeric acid and dibasic acid.

In Table 2, the properties of esters of oleic acid and trimethylolpropane and esters of mixed fatty acid and trimethylolpropane containing 5 parts by weight of dimer acid in oleic acid were compared.

Wherein R1, R2 are hydrogen or the same or different alkyl group.

[Table 2]

Example 4 Manufacture of Hydraulic Hydraulic Oil

About the base compound obtained in Example 3, it mix | blended as Table-3 and measured the property. The results are shown in Table-4.

As described in detail above, the hydraulic oil composition of the present invention improves the properties of conventional petroleum lubricants, and partially polymerizes mixed acids of higher fatty acids with complex alcohol to minimize the viscosity drop due to diversification of base viscosity and shearing. It is effective in providing a new synthetic lubricant that has been successful.

The present invention has the effect of better flash point, pour point, viscosity index, oxidation stability, abrasion resistance, and load resistance than conventional petroleum lubricants or conventional polyol ester synthetic lubricants. It is possible by appropriately adjusting the conditions when reacting with Ⅲ) and (IV), and since they maintain chemical bonds, they have the effect of eliminating the phenomenon of viscosity drop during the administration of a simple polymer thickener.

Claims (2)

In a hydraulically actuated hydraulic composition produced by mixing a defoamer thickener, a flame retardant, etc. with a base such as a polyol ester, A hydraulic hydraulic oil composition using a partially polymerized polyol ester by reacting a saturated or unsaturated fatty acid having 6 to 24 carbon atoms of the following formula (1) with a mixed alcohol and a nitrogen atmosphere at a temperature of 130 to 270 ° C for 10 to 30 hours. In formulas (1) and (2), R is a saturated or unsaturated alkyl group having 2 to 11 carbon atoms which are the same or different, X1 is a bond between two molecules, X2 is a bond between three molecules, and in formula (3), n is an integer of 1-12. In formula 4, R1, R2 are the same or different alkyl group having 1 to 4 carbon atoms or (CH2) nOHn is the same or different integer from 1 to 2. The method of claim 1, When two or more polyol ester bases are mixed and used, a hydraulic base oil composition in which a main base (50.1 to 99.9 parts by weight) and other bases (0.1 to 49.9 parts by weight) is added as a performance improving agent. In formula (5), R3 is hydrogen or an alkyl group having 1 to 10 carbon atoms.