KR920009624B1 - Water-glycol fluid containing aliphatic carboxylic acids - Google Patents

Abstract

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Description

Aliphatic carboxylic acid-containing water-glycol fluid

The present invention relates to energy transmitting fluids, in particular water-glycol type energy transmitting fluids having modified lubricity and wear resistance under high pressure conditions.

Water-based fluids have been used commercially as a means of transmitting energy in hydraulics for many years.

Among these water-based fluids are, for example, water-soluble glycols or glycols described in US Pat. Nos. 2,558,030 and 2,602,780 to Zisman et al. And US Pat. No. 2,768,141 to Langer et al. Ether-containing compositions (hereinafter referred to as "water-glycol" type fluids).

Compared to petroleum-based fluids, water-glycol type fluids generally have low combustion and good temperature stability. Also, unlike the use of petroleum-based compositions, cleaning and disposal are more convenient when using water-glycol type fluids. However, water-glycol type energy transfer fluids such as those described in the above-mentioned patents generally have relatively low lubricity and wear resistance in high pressure applications.

In an attempt to improve the properties of water-glycol type energy transfer fluids, various lubricity and / or wear resistant additives have been introduced.

US Pat. No. 2,947,699 to Wasson et al. Describes the use of alkali metal soaps of organic fatty acids as abrasion resistant in water-glycol type hydraulic fluids.

US Pat. No. 4,493,775 to Snyder, Jr. et al. Describes water-based hydraulic fluids containing metal or amine salts of organic sulfur, phosphorus, boron or carboxylic acids as antiwear or lubricants.

U.S. Patent No. 3,992,312 to Genjida et al. Provides about 30 to 60 weight percent water; About 5 to 30% by weight of a water-soluble polymer containing (1) residues of a polyamide having an active hydrogen atom and (2) an oxyalkylene group bonded to the residue; And about 15 to 60 weight percent glycol, and a water-glycol basic hydraulic fluid is described that has good lubrication and wear protection properties.

Lewis, US Pat. No. 4,434,066, discloses about 0.1 to 10% by weight of acidic lubricants (ie, saturated and unsaturated carboxylic acids and polycarboxylic acids having 6 or more carbon atoms, aromatic carboxylic acids, alkali metal or organic amine salts of these carboxylic acids, polymerized) Water-glycol type fluid compositions containing fatty acids, oxycarboxylic acids and dicarboxylic acids) and about 0.01 to about 10 weight percent of an antiwear agent (i.e., a compound of a hydroxyl-substituted aromatic acid component and a nitroaromatic compound component) are described. .

US Patent 4,390,439 to Schwartz et al. Describes the use of neodecanoic acid to improve the wear resistance and corrosion-inhibiting properties of hydraulic fluids containing water in an amount of about 60 to about 99% by weight.

Although specifications in the art previously published prior to the present disclosure contemplate improved lubricity and wear resistance of additive-containing fluids, the lubricity and abrasion of water-glycol type fluids allow the use of such fluids in systems operating under pressures of less than about 3,000 psi. It has been limited.

Thus, it is an object of the present invention to provide a water-glycol type energy transfer fluid with improved high pressure performance.

Useful for system operation under a pressure of about 5,000 psi or less of the present invention, comprising: (a) about 30 to about 40, preferably about 34 to about 37 weight percent water, based on the total weight of the fluid; (b) diethylene glycol; (c) from about 0.8 to about 5.0 weight percent aliphatic carboxylic acid, based on the total weight of the fluid, of 9 to 12 carbon atoms; (d) water-soluble polymeric viscosity modifiers; (e) one or more corrosion inhibitors; And (f) a metal desulfurizing agent, wherein (b) and (d) are present in an amount sufficient to provide a fluid having a viscosity of about 10 to about 200 centistokes at 40 ° C. It is about.

The invention also relates to a method of transferring mechanical energy by fluid pressure in a system operating under a pressure of about 5,000 psi or less when using the fluid referred to herein as an energy transfer medium.

Certain mixtures of water, diethylene glycol, and carboxylic acids described herein are effective for improving the high pressure performance of water-glycol type energy transfer fluids and are more than about 5,000 psi, preferably about 7,000 psi, It has been found useful to use systems that preferably operate at pressures of about 10,000 psi or less.

According to the invention, it has a viscosity of about 10 to about 200 centistokes at 40 ° C. with water, diethylene glycol, aliphatic carboxylic acids having 9 to 12 carbon atoms, water-soluble polymeric viscosity modifiers, at least one corrosion inhibitor and metal deactivator A water-glycol composition containing is provided.

The aliphatic carboxylic acid component of the composition of the present invention is selected from saturated and unsaturated, straight and branched carboxylic acids and polycarboxylic acids having 9 to 12 carbon atoms and mixtures thereof. Representative carboxylic acids useful in the present invention are nonanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, dodecanoic acid and mixtures thereof.

For the present invention C ₉ to C ₁₂ carboxylic acids are generally from about 0.8 to about 5.0% by weight, preferably from about 1.0 to about 2.0% by weight, most preferably based on the total weight of the above-mentioned compositions It is present in an amount of about 1 to about 1.6% by weight. At concentrations below about 0.8% by weight, C ₉ to C ₁₂ carboxylic acids generally cannot provide the lubricity required for high pressure action.

For the purposes of the present invention, C ₁₀ to C ₁₂ linear carboxylic acids are preferred carboxylic acids.

Polymeric viscosity modifiers in the compositions of the present invention are poly (alkylene oxide) polymers, alkylene oxide adducts of alkyl phenols, polyalkyl methacrylates, urethane polymers, polyamide esters and polyamide alkoxylates, and poly (alkylene Oxide) polymers are preferred polymers.

Poly (alkylene oxide) polymers useful in the present invention contain random or block distributions of oxyethylene groups or two oxyethylene groups, and higher oxyalkylene groups such as oxypropylene and oxybutylene groups and contain about 400 to about 40,000 Or higher average molecular weight. The amount of organoethylene groups in the molecule is such that the poly (alkylene oxide) polymer is dissolved in water at 25 ° C., and the amount of oxypropylene or higher oxyalkylene group is less than 40,000 at 25 ° C. of poly (alkylene oxide). Until the amount is maintained in liquid. The oxypropylene / oxyethylene ratio can vary from zero to about one. These poly (alkylene oxide) polymers are ethylene oxide or mixtures of ethylene oxide and propylene oxide or higher alkylene oxide compounds having from 1 to 6 active oxygen atoms, for example water, monohydroxy alcohols such as ethanol And propanol), dihydroxyl alkyl (e.g. ethylene glycol), trihydroxyl alkyl (e.g. glycerin and trimethylpropane), tetrahydroxyl alkyl (e.g. pentaerythritol), hexa hydroxyl alcohol (e.g. sorbitol) and It can be prepared by methods known in the art to react with mono or polyfunctional amines such as butylamine and ethylene diamine. The poly (alkylene oxide) product of this reaction will be either straight or branched oxyethylene or oxyethylene-higher oxyalkylene chains, which chains will be terminated with hydroxyl groups. Some or all of these hydroxyl groups may be esterified by reaction with dialkyl sulfates such as diethylsulfate.

Alkylene oxide adducts of alkyl phenols suitable for use in the present invention are, for example, adducts described in US Pat. No. 2,768,141 to Langer et al. And US Pat. No. 3,379,644 to Katzenstein et al.

Polyalkyl methacrylates and polyurethanes that can be used in the present invention are described, for example, in US Pat. No. 3,352,783 to McCord. These polyalkyl methacrylates are generally prepared by polymerizing alkyl methylacrylates in which the alkyl group has on average about 3 to about 10 carbon atoms.

Polyamide esters useful in the present invention include the polymers described in Shibe, U.S. Patent No. 3,341,573. Suitable polyamide alkoxylates are described, for example, in US Pat. No. 3,992,312 to Genjida et al.

For the present invention, it has a viscosity of up to about 100,000 centistokes at 100 ° C., preferably from about 5,000 centimeters to about 50,000 centistokes at 100 ° C., and contains from about 65 to about 85 weight percent of oxyethylene groups, Random copolymers of ethylene oxide and 1,2-propylene oxide are preferred.

It will be apparent to those skilled in the art that the relative amounts of the provided viscosity modifier and diethylene glycol for the energy transfer composition of the present invention will vary depending upon the viscosity of the desired energy transfer composition and the particular viscosity control agent used therein. . Preferably, diethylene glycol and viscosity modifier are present in the compositions of the present invention in an amount sufficient to provide the composition with a viscosity of about 35 to about 80 centistokes at 40 ° C. In general, the composition viscosity within the above-mentioned preferred ranges is achieved by using about 10 to 20 weight percent poly (alkylene oxide) viscosity modifier and about 40 to 60 weight percent diethylene glycol based on the weight of the composition.

The optimum viscosity of the fluid composition of the present invention is variously determined and somewhat dependent on the type of pump used in a given operation. For example, a vane pump typically operates at a pressure of about 3,000 psi or less and uses a composition having a viscosity of about 60 to about 80 centistokes at 40 ° C. as the fluid of choice, while generally about Fluids selected from axial piston pumps operating under pressures from 5,000 psi to about 6,000 psi typically have a viscosity of about 35 to about 50 centistokes at 40 ° C.

Corrosion inhibitors useful in the compositions of the present invention include alkylamines (e.g. propylamine, butylamine, hexylamine, n-octylamine, cyclohexylamine, dimethylaminopropylamine, etc.), alkanolamines (e.g. ethanolamine, triethanolamine , N, N-dimethylethanolamine), arylamines (such as aminotoluene), other amine-type corrosion inhibitors (such as ethylene diamine, isopropylaminoethanol, tripropylamine, morpholine, pyridine, 1,4- Bis (2-aminoethyl) piperidine, imidazoline, 2-heptadecyl-1- (2-hydroxyethyl) -imidazoline, etc.) and mixtures thereof. In addition to the amine type corrosion inhibitors, other corrosion inhibitors useful in the present invention include alkali metal nitrites, nitrates and benzoates, alkoxylated fatty acids, and mixtures thereof.

The amount of corrosion inhibitor present in the compositions of the present invention is varied and depends in part on factors including the choice of inhibitor (s) and the strength of the process using the fluid. Generally, the total amount of inhibitor present in the composition of the present invention is about 0.4 to about 4.0 weight percent based on the total weight of the composition. As used herein, the "corrosion inhibiting amount" of an inhibitor is greater than or equal to the amount of one or more inhibitors effective to achieve the degree of corrosion protection required for a particular process.

The metal deactivators used in the present invention serve primarily as chelating agents for copper and copper alloys. Representative metal deactivators useful in the compositions of the present invention include tolyltriazole, benzotriazole, mercaptobenzothiazole, sodium mercapto benzothiazole, disodium 2,5-mercaptothiadiazole, mercaptobenzoimidazole and the like. Mixture. Generally, the total amount of metal deactivator present in the composition of the present invention is about 0.01 to about 2.0 weight percent based on the total weight of the composition.

In addition to the aforementioned components, the energy transfer fluids of the present invention may further contain one or more additional components commonly used in water-based fluids. When containing these components, their total amount is usually from about 0.001 to about 2% by weight, based on the total weight of the liquid fluid composition.

Examples of such additional components are foam inhibitors (e.g. silicones in emulsifier form, polyoxyalkylene-type nonionic surfactants, etc.), alkaline affinity dyes, metal ion sequestrants [e.g. ethylene diaminetetraacetic acid (EDTA), diethylenetri Aminocarboxylic acids and derivatives thereof, including amine acetic acid, sodium or copper salts thereof, oxycarboxylic acids and derivatives thereof (e.g., tartaric acid and sodium glyconate), and other components mentioned above to improve the lubricity of the resulting composition. Additives that do not adversely affect.

In preparing the water-based compositions of the present invention, each of the ingredients used may be prepared in any order of participation, or some of these mixtures may be prepared prior to the same addition into the composition. In general, each component used should be in a water-soluble form, such as an alkali metal or ammonium salt thereof, or dissolved in situ. The compositions of the present invention can be prepared from concentrates which, when used, are diluted to give the abovementioned water content.

According to a preferred embodiment of the invention, (a) about 34 to about 37 weight percent water, based on the total weight of the fluid, (b) about 12 to about 16 weight percent number, based on the total weight of the fluid Soluble polyalkylene oxide viscosity modifiers, preferably ethylene having a viscosity of from about 40,000 to about 60,000 centistokes at 100 ° C. and containing from 70 to about 80 weight percent of ethylene oxide groups based on the total weight of the copolymer A copolymer of oxide and propylene oxide, (c) about 1.0 to about 2.0 weight percent linear aliphatic carboxylic acid, preferably tecanoic acid and / or dodecanoic acid, based on the total weight of the fluid, (d) about 35 to about 40 weight percent diethylene glycol, based on the total weight of the fluid, (e) about 1.4 to about 3.5 weight percent of one or more amine-type corrosion inhibitor, based on the total weight of the fluid, wind Preferably a mixture of about 0.6 to about 1.5 weight percent morpholine and about 0.8 to 2.0 weight percent isopropyl aminoethanol based on the total weight of the fluid, and (f) the total weight of the fluid On the basis of this, there is provided an energy transfer fluid useful for systems operating under a pressure of about 5,000 psi or less, essentially containing about 0.04 to 0.1 weight percent metal deactivator, preferably tolyltriazole.

The following examples illustrate the invention but are not intended to limit the scope thereof. Unless otherwise stated, all percentages are by weight.

[Examples 1 to 3 and Comparative Examples C ₁ to C ₂ ]

High-pressure performance of fluids prepared as shown in Table (I) is a method named “Standard Method for Measuring the Wear Characteristics of Petroleum and Non-Petroleum Hydraulic Fluids in Constant Volume Vane Pumps” mentioned in ASTM D 2882-83. Is measured accordingly. The operating conditions used in the test were as follows:

The procedure referred to in ASTM D 2882-83 is repeated six times for each composition. The fluid wear rate is obtained according to each test run given. The wear rate is obtained as a reduction in the total weight of the cam ring and vanes of the pump after the test run time.

The wear rates given in table (I) are averages of the six repeated test runs. The composition is considered to have passed the test if it provides a wear rate of less than 1 g / 100 hour for each of six repeated operations. Abrasion rates in excess of 1 g / 100 hour are provided and the operation is stopped and the composition is considered failed.

Vickers V-104C Vane Pump

Pump speed 1200rpm

Pump Pressure 1900 psig (134 kg / cm ² )

Fluid speed 65 ℃

2 gallons of fluid

100 hours operating time

Table (I)

1. In addition to the components mentioned above, less than about 0.01% by weight of benzoic acid is included in each of the compositions set forth in Table (I).

2. Test results for Composition C ₂ are based on a single pump test run.

3. Less than 1 g / 100 hours of wear appeared in five of the six test runs for Composition 3, and more than 1 g / 100 hours of wear in the sixth run.

4. Available as Union Carbide Corporation, with 380,000 S.U.S. at 100 ° F (37.8 ° C). Ethylene oxide and propylene oxide linear polymers containing 75% by weight of oxyethylene and 25% by weight of oxypropylene, having a viscosity.

Example 4

The performance of fluids prepared according to composition (2) in Table (I) under 5,000 psi operating input is divided into the following test regimes: the start time of 2 hours, the burst time of 1 hour and the test time of 222 hours. Measure accordingly.

16 gallons of test fluid is filled into a Sunstrand Model 22-2132, multiple flow pump equipped with a welding piston. The operating conditions used in the test were as follows:

Pressure speed 3100 ± 100l.p.m

Load pressure 5000psi

Conversion pressure 200 ± 20psi

Case pressure up to 40 psi

Stroke half

Storage temperature 120 ± 10 ℉

Loop temperature 170 ± 10 ° F

Suction vacuum 10 inch Hg (5 psi)

Read test flow data over time. In accordance with the test, a drop in flow rate indicates system wear (ie, system wear as a space between the flow system parts is reduced and the flow rate of the fluid is slowed). Flow data for this test is shown in Table II. Examination of the flow data in the chart shows no significant drop in flow after the test run time.

After a 222 hour test period, the system is cooled to a loop temperature of 100 ° F. and closed. After 24 hours of closing, the pump is disassembled to observe wear. Examination of the test part shows no special wear or breakage.

TABLE (II)

Claims (15)

Based on the total weight of the fluid: (a) 30-40 weight percent water, (b) 40-60 weight percent diethylene glycol, (c) 0.8-5.0 weight percent aliphatic carboxylic acid having 9 to 12 carbon atoms, at 40 ° C., containing (d) from 10 to 20% by weight of a water-soluble polymeric viscosity modifier, (e) from 0.4 to 4.0% by weight of at least one corrosion inhibitor, and (f) from 0.01 to 2.0% by weight of metal deactivator Energy transmitting fluid having a viscosity of 10 to 200 centistokes. The fluid of claim 1 wherein the polymeric viscosity modifier is selected from poly (alkylene oxide) polymers, alkylene oxide adducts of alkyl phenols, poly alkyl methacrylates, urethane polymers, polyamide esters, and polyamide alkoxylates. . The fluid of claim 2 wherein the corrosion inhibitor contains one or more amine type corrosion inhibitors. The metal deactivator according to claim 3, wherein the metal deactivator is tolyltriazole, benzotriazole, mercaptobenzothiazole, sodium mercaptobenzothiazole, disodium 2,5-mercaptothiadiazole, mercaptobenzoimidazole and mixtures thereof. Fluid selected from among. The fluid of claim 1 or 4, wherein the water-soluble polymeric viscosity modifier is a poly (alkylene oxide) polymer. The fluid of claim 5, wherein the poly (alkylene oxide) polymer is a random copolymer of ethylene oxide and 1,2-propylene oxide having a viscosity of 100.000 centistokes or less at 100 ° C. 7. The fluid of claim 1 wherein the carboxylic acid is selected from nonanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, dodecanoic acid, and mixtures thereof. The fluid of claim 1 containing as a amine-type corrosion inhibitor a mixture of morpholine and isopropylamino ethanol. (A) 34 to 37 weight percent mole, (b) 12 to 16 weight percent water-soluble poly (alkylene oxide) viscosity modifier based on the total weight of the fluid, (c) 1.0 to 2.0 weight percent carbon number 9 to 12 aliphatic carboxylic acids, (d) 35 to 50 weight percent diethylene glycol, (e) 1.4 to 3.5 weight percent amine-type corrosion inhibitor, and (f) 0.04 to 0.1 weight percent metal deactivator Energy transfer fluid containing. The fluid of claim 9 wherein the poly (alkylene oxide) viscosity modifier has a viscosity of 40,000 centistokes to 60,000 centistokes at 100 ° C. and contains 70 to 80 percent by weight of ethylene oxide groups. 10. The fluid of claim 9 containing as a amine-type corrosion inhibitor a mixture of morpholine and isopropylamino ethanol. The fluid of claim 11, wherein the metal deactivator is tolyltriazolin. 13. The fluid of claim 12, wherein the aliphatic carboxylic acid is 10 to 12 carbon atoms. The fluid of claim 13 wherein the aliphatic carboxylic acid is decanoic acid, dodecanoic acid or a mixture thereof. A method for transferring mechanical energy by fluid pressure when operating the system under pressure of up to 5,000 psi, characterized by using the fluids mentioned in claims 1, 4, 9 or 12 as energy transfer medium.