CN102695785A - Flame-retardant hydraulic oil composition - Google Patents

Flame-retardant hydraulic oil composition Download PDF

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CN102695785A
CN102695785A CN2010800612135A CN201080061213A CN102695785A CN 102695785 A CN102695785 A CN 102695785A CN 2010800612135 A CN2010800612135 A CN 2010800612135A CN 201080061213 A CN201080061213 A CN 201080061213A CN 102695785 A CN102695785 A CN 102695785A
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acid
ester
oil
quality
amount
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CN102695785B (en
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三本信一
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Eneos Corp
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JX Nippon Oil and Energy Corp
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    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
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    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
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Abstract

Disclosed is a flame-retardant hydraulic oil which has a satisfactory antioxidant activity, an excellent inhibitory activity on the elution of zinc and good abrasion resistance, can respond to the increase in pressure and the tendency to be maintainance-free in hydraulic systems in recent years, and has a long service life. Specifically disclosed is a flame-retardant hydraulic oil composition comprising (A) at least one base oil selected from the group consisting of synthetic esters, oils and fats each of which is characterized in that the content ratio of an unsaturated fatty acid in fatty acid in fatty acids that constitute the ester moiety is 20 mol% or more and the acid value of the ester moiety is 1.0 mgKOH/g or less and (B) an alkylthiadizole in an amount of 0.001 to 1.0 mass% relative to the total amount of the composition. Preferably, the composition additionally comprises (C) a bis(4-dialkylaminophenyl)methane in an amount of 0.001 to 5.0 mass% relative to the total amount of the composition and/or (D) at least one triazole compound selected from the group consisting of a triazole derivative, a benzotriazole derivative and a tolutriazole derivative in an amount of 0.0001 to 1.0 mass% relative to the total amount of the composition.

Description

The flame retardant resistance hydraulic fluid compositions
Technical field
The present invention relates to the flame retardant resistance hydraulic fluid compositions; Relate more specifically to such flame retardant resistance hydraulic fluid compositions; It is suitable for the application of use under the high-temperature and high-pressure conditions with high fire occurrence risk property most; As be used for aluminum dipping form casting forcing machine or the operation of iron work equipment, and it is applicable to attrition resistance, the excellent HPP of sludge inhibition and particularly zinc stripping inhibition, and it can be used for a long time.
Background technology
Usually, as the hydraulicefficiency oil as using in the operation in aluminum dipping form casting forcing machine or iron work equipment that under the place with high fire occurrence risk property, uses, flame retardant resistance hydraulicefficiency oil (liquid) has been used to keep the security in place like water-ethylene glycol or fatty ester.Especially in the place that is limited by the restriction of fire service law the 4th petroleum-type, mainly use water-ethylene glycol liquid, but have about the loaded down with trivial details storage of waste oil and the shortcoming of attrition resistance.Yet the modification of fire service law in 2002 makes the hydraulicefficiency oil with flash-point more than 250 ℃ get rid of outside the fire service law scope, causes having relatively more extensively using of the fatty ester of high flash point.As a result, ester oil has just become flame retardant resistance hydraulicefficiency oil jointly.
The character of fatty ester changes according to the lipid acid composition that constitutes ester.The oxidative stability of the ester of sfas is more excellent.Yet sfas is produced through the unsaturated fatty acids that synthetic petroleum raw material or hydrogenation are derived from vegetable and animals oils, thereby is to the disagreeableness expensive raw material of environment.At present, also used natural synthetic ester or grease, it mainly contains the lipid acid (referring to following patent documentation 1-3) that comprises the unsaturated fatty acids that is derived from vegetable and animals oils favourable on environmentally friendly and the cost.
Simultaneously, because nearest hydraulicefficiency system is used under elevated pressures and need do not safeguarded more than becoming in the past, therefore, the hydraulicefficiency oil that requires to use in these cases has long lifetime property and excellent attrition resistance.The natural synthetic ester of being produced by natural materials such as vegetable and animals oils contains the lipid acid that mainly is made up of unsaturated fatty acids, thereby to favourable on global environment close friend and the cost.Yet it is being extremely poor shortcoming aspect oxidative stability of the synthetic ester of sfas or synthetic hydrocarbon oil.
In principle, because ester class hydraulicefficiency oil is understood stripping zinc through remaining lipid acid, so do not use zinc at part such as pipeline, valve or the joint etc. of contact oil.Yet,, wherein cause quantity increase such as the situation of the problem that forms sludge from zinc in the zinc-plated part stripping that is generally used for the pipeline of hydraulicefficiency system, valve or joint being widely used down of ester class flame retardant resistance hydraulicefficiency oil.Especially, residual water promotes the stripping of zinc when water-ethylene glycol hydraulicefficiency oil changes ester class hydraulicefficiency oil into, thereby takes place in large quantities such as the problem of filter stoppage etc.Also bring the stripping of zinc through the acid that increases along with oily deterioration, thereby be used for the measurement of zinc stripping, oil oxidation stability also becomes important factor.
For conventional mineral hydraulicefficiency oil or synthin hydraulicefficiency oil, phenols or amine antioxidants or ZnDTP (zinc dialkyl dithiophosphate) have been used.Yet the ester class hydraulicefficiency oil that comprises saturated or unsaturated fatty acids has the problem that is difficult to prolong working life, adds this type of conventional phenols or the amine antioxidants oxidation-resistance also will be inadequate even this is.
Especially, this trend is being used in the synthetic ester of unsaturated fatty acids production bad aspect the oxidative stability or vegetable and animals oils as being significant under the basic oil condition.Because do not find as yet for this type of by the synthetic ester of unsaturated fatty acids production or the additive of vegetable and animals oils useful effect; Therefore can only select synthetic ester (it influences global environment and costliness unfriendly) usually by sfas production; The synthetic ester or the vegetable and animals oils (its oil change interval is short) of perhaps producing by unsaturated fatty acids, and do not have other selection.
For conventional mineral hydraulicefficiency oil, ZnDTP or aromatic phosphoric ester also use as the abrasion resisting additive.Yet, point out following problem for containing ester as the hydraulicefficiency oil of base oil, because therefore the high adsorption activity of ester is compared with being used for mineral hydraulic pressure oil condition, additive seldom plays effect.For example, the TCP (Tritolyl Phosphate) as typical Phosphorus abrasion resisting additive can show the abrasion resisting effect hardly in fatty ester.
Except the problems referred to above, the problem that produces recently is the zinc-plated stripping through the acid that exists in the ester hydraulicefficiency oil or between its usage period, produce that in hydraulicefficiency system, is applied to pipeline or valve.Up to now, do not produce the technology that suppresses the zinc stripping, and do not use the zinc-plated best measure of thinking.
As stated, in the present circumstance, using the synthetic ester produced by environmentally friendly and relatively cheap natural matter or vegetable and animals oils to develop attrition resistance, excellent to prolong the flame retardant resistance hydraulicefficiency oil of working life thus very difficult with suppressing the zinc stripping.
Reference listing
Patent documentation
Patent documentation 1: Japanese Patent Laid is opened communique 2001-214187
Patent documentation 2: jp patent publication 3548591
Patent documentation 3: jp patent publication 2888747
Summary of the invention
The problem that invention will solve
In synthetic ester, some unreacted lipid acid are remaining and cause the stripping of zinc.When the acid number of lipid acid is too high, suppress the effect reduction of the additive of zinc stripping.When the lipid acid that forms ester was sfas, it was poorly soluble thereby make the zinc of metal such as stripping and deterioration product precipitate (settle) easily, forms sludge then.
Though add extreme-pressure additive for suppressing abrasive purpose, gentle extreme-pressure additive such as SULPHOSUCCINIC ACID ESTER are invalid in ester.Otherwise, have strong active extreme-pressure additive oxidative stability and sludge inhibition had disadvantageous effect and often cause the zinc stripping.
In addition, oxidative stability also is to suppress the material particular of zinc stripping.For the hydraulicefficiency oil that contains ester, it is poor as basic oil oxidation stability, and acid number increases between its usage period, thereby promotes the zinc stripping.Yet the conventional phenols or the amine antioxidants that have been used for MO or synthetic hydrocarbon oil can not provide ester oil with sufficient antioxidant effect.
In view of the foregoing carry out the present invention; And purpose is to provide more persistent flame retardant resistance hydraulic fluid compositions; It comprises that mainly containing unsaturated fatty acids and acid number has sufficient oxidation-resistance and good zinc stripping inhibition and attrition resistance and response at the unsaturated fatty acids below the particular value or vegetable and animals oils and its and increase and non-maintaining trend at the pressure in the hydraulicefficiency system in recent years.
The scheme that is used to deal with problems
As the result who investigates further and study; The present invention is based on accomplishing to the discovery that base oil solves the problems referred to above through adding the special metal corrosion inhibitor, said base oil for particularly in the lipid acid that constitutes ester, comprise 20 moles more than the % the unsaturated fatty acids that is derived from natural matter and to have acid number be synthetic ester and/or grease below the 1.0mgKOH/g.In addition, the mixing with specific amine oxidation retarder and/or specific nitrogen based metal deactivators of excellent anti-oxidation characteristics causes the exploitation of ester class flame retardant resistance hydraulicefficiency oil, and it has the work-ing life that further prolongs.
The value that " acid number " expression of here using is measured according to JIS K2501 " TP is counted in the neutralization of petroleum products and lubricating oil " (potentiometric titration).
Promptly; The present invention relates to the flame retardant resistance hydraulic fluid compositions; It comprises that (A) is selected from least a base oil of the group of being made up of synthetic ester and grease; Said synthetic ester and grease in constituting the lipid acid of ester, comprise 20 moles more than the % unsaturated fatty acids and to have acid number be below the 1.0mgKOH/g and (B) the alkyl thiadiazoles of the amount of 0.001-1.0 quality %, based on the compsn total mass.
The invention still further relates to aforementioned flame retardant resistance hydraulic fluid compositions, it further comprises: (C) two (4-dialkylamino phenyl) methane of the amount of 0.001-5.0 quality % by following formula (1) expression, based on the compsn total mass:
Figure BDA00001875862200051
R wherein 1, R 2, R 3And R 4Can be same to each other or different to each other, and independently of one another for having the alkyl of 1-6 carbon atom.
The invention still further relates to aforementioned flame retardant resistance hydraulic fluid compositions; It further comprises: (D) at least a triazole compounds that is selected from the group of forming by triazole derivative, OR 10154 and tolytriazole verivate of the amount of 0.0001-1.0 quality %, and based on the compsn total mass.
The effect of invention
According to the present invention; For the base oil of the ester oil of the lipid acid that mainly comprises unsaturated fatty acids and special metal corrosion inhibitor or further special antioxidants and/or nitrogen based metal deactivators mixes, provide not only oxidative stability with attrition resistance is good but also can suppress the zinc stripping and in the FZG gear is tested, pass through the flame retardant resistance hydraulic fluid compositions in 10 above stages thus.
Embodiment
Below the present invention will be described in more detail.
The base oil that is used for flame retardant resistance oil compsns of the present invention is at least a base oil that is selected from the group of being made up of synthetic ester and grease, said synthetic ester and grease group each self-contained 20 moles of unsaturated fatty acids of measuring more than the % and to have acid number be below the 1.0mgKOH/g in the lipid acid of formation ester.The instance that should synthesize ester comprises fatty ester, polyol ester and complex ester.Greasy instance comprises various animal-plant oil.Preferably having 40 ℃ of following kinematic viscosity is 10-200mm 2/ s and flash-point are those more than 280 ℃.
The preferred embodiment of fatty ester comprises unsaturated fatty acids such as Zoomeric acid, oleic acid, vaccenic acid, linolic acid, linolenic acid, eleostearic acid and 8; 11-eicosadienoic acid and have sfas such as valeric acid, caproic acid, enanthic acid, sad, n-nonanoic acid, capric acid, undeeanoic acid, laurostearic acid, tridecylic acid, TETRADECONIC ACID, pentadecanoic acid, palmitic acid, margaric acid, the stearic acid and the nonadecanoic acid of the straight or branched alkyl that contains 5-19 carbon atom and have the monohydroxy-alcohol of the straight or branched alkyl that contains 1-15 carbon atom such as the ester of methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, hexanol, enanthol, octanol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, tridecanol, tetradecyl alcohol and pentadecanol; With its mixture.Concrete preferred examples comprises the ester of fatty ester such as Triple Pressed Stearic Acid and oleic mixed fatty acid and butanols and the ester of Triple Pressed Stearic Acid and lauric mixed fatty acid and octanol.
Polyol ester preferably has divalent alcohol or the polyvalent alcohol and the ester with lipid acid of 1-24 carbon atom of 3-20 hydroxyl.
The specific examples of divalent alcohol comprises terepthaloyl moietie, 1, ammediol, Ucar 35,1,4-butyleneglycol, 1,2-butyleneglycol, 2-methyl isophthalic acid, ammediol, 1; 5-pentanediol, NSC 6366,1,6-pinakon, 2-ethyl-2-methyl isophthalic acid, ammediol, 1,7-heptanediol, 2-methyl-2-propyl group-1; Ammediol, 2,2-diethylammonium-1, ammediol, 1,8-ethohexadiol, 1; 9-nonanediol, decamethylene-glycol, 1,11-undecane two is pure and mild 1, the 12-dodecanediol.
The specific examples of polyvalent alcohol (polyols) comprises that polyvalent alcohol (polyhydric alcohols) is like trimethylolethane, TriMethylolPropane(TMP), tri hydroxy methyl butane, two-(TriMethylolPropane(TMP)), three-(TriMethylolPropane(TMP)), tetramethylolmethane, two-(tetramethylolmethane), three-(tetramethylolmethane), glycerine, poly-glycerol (dimer to two of glycerine ten aggressiveness (eicosamer)), 1; 3,5-penta triol, Sorbitol Powder, sorbitan, Sorbitol Powder-glycerol condensate, adonitol, arabitol, Xylitol and mannitol; Carbohydrate such as wood sugar, pectinose, ribose, rhamnosyl, glucose, fructose, semi-lactosi, seminose, sorbose, cellobiose, SANMALT-S, isomaltose, trehalose, sucrose, raffinose, gentianose and melizitose; The product of its partial esterization; And methyl glucoside (glycosides).
In these; Preferred polyhydric alcohols be hindered alcohols (hindered alcohols) like NSC 6366, trimethylolethane, TriMethylolPropane(TMP), tri hydroxy methyl butane, two-(TriMethylolPropane(TMP)), three-(TriMethylolPropane(TMP)), tetramethylolmethane and two-(tetramethylolmethane), this is because their excellent stability to hydrolysiies.
The instance of the lipid acid of polyol ester comprises the unsaturated fatty acids and the sfas with the straight or branched alkyl that contains 5-19 carbon atom about above-mentioned fatty ester example.The preferred especially unsaturated fatty acids that uses about above-mentioned fatty ester example.Can also use the eo-acid of alpha-carbon atom as quaternary carbon.The specific examples that props up chain saturated fatty acid comprises isovaleric acid (3 Methylbutanoic acid), 2 methyl caproic acid, 2-ethyl valeric acid, 2 ethyl hexanoic acid and 3,5,5 Trimethylhexanoic acid.
The specific examples of preferred polyhydric alcohols ester comprises diester, three esters and four esters of one or more lipid acid and polyvalent alcohol; Said one or more lipid acid are selected from by unsaturated fatty acids such as Zoomeric acid, oleic acid, vaccenic acid, linolic acid, linolenic acid, eleostearic acid and 8; The 11-eicosadienoic acid; The group of forming with the sfas with the straight or branched alkyl that contains 5-19 carbon atom such as valeric acid, caproic acid, enanthic acid, sad, n-nonanoic acid, capric acid, undeeanoic acid, laurostearic acid, tridecylic acid, TETRADECONIC ACID, pentadecanoic acid, palmitic acid, margaric acid, stearic acid and nonadecanoic acid; And comprise unsaturated fatty acids, said polyvalent alcohol such as NSC 6366, trimethylolethane, TriMethylolPropane(TMP), tri hydroxy methyl butane or tetramethylolmethane.
The ester of two or more lipid acid can be mixture, perhaps two or more mixed fatty acids and the ester of polyvalent alcohol of the ester of two or more a kind of lipid acid and polyvalent alcohol.
In these polyol esters; The ester of preferred following hindered alcohols; Said hindered alcohols such as NSC 6366, trimethylolethane, TriMethylolPropane(TMP), tri hydroxy methyl butane, two-(TriMethylolPropane(TMP)), three-(TriMethylolPropane(TMP)), tetramethylolmethane, two-(tetramethylolmethane) and three-(tetramethylolmethane); The more preferably ester of NSC 6366, trimethylolethane, TriMethylolPropane(TMP), tri hydroxy methyl butane and tetramethylolmethane also, this is because their excellent stability to hydrolysiies.The ester of TriMethylolPropane(TMP) and tetramethylolmethane most preferably, this is because their excellent especially stability to hydrolysiies.Specific examples comprises oleic acid and the sad mixed fatty acid and the ester of TriMethylolPropane(TMP); The mixed fatty acid of oleic acid and n-nonanoic acid and the ester of TriMethylolPropane(TMP); Oleic acid and sad mixed fatty acid and ester and the mixed fatty acid of oleic acid and n-nonanoic acid and the ester of tetramethylolmethane of tetramethylolmethane.
Polyol ester can keep nonesterified partial ester or whole esterified full ester of hydroxyl wherein for a part of hydroxyl wherein.In addition, polyol ester can be the mixture of partial ester with full ester, but preferred full ester.
Complex ester is the ester of lipid acid and diprotic acid and monohydroxy-alcohol and polyvalent alcohol.Lipid acid, monohydroxy-alcohol and polyvalent alcohol can be for about those of above-mentioned polyol ester example.
The instance of diprotic acid comprises the diprotic acid with 5-10 carbon atom, like pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid and sebacic acid.
Be used for ester of the present invention and can be having single structure a kind of ester those or have the mixture of the two or more ester of different structure.
In these synthetic esters, the preferred polyol ester, this is because their excellent stability to hydrolysiies.
The greasy instance that is used as the base oil of flame retardant resistance hydraulic fluid compositions of the present invention comprises natural animal or Vegetable oil lipoprotein, like rapeseed oil, sunflower oil, VT 18, Viscotrol C, Oleum Cocois, Semen Maydis oil, Oleum Gossypii semen, sweet oil, Rice pollard oil, plam oil, palm-kernel oil, peanut oil, Yatall MA, butter, lard and its hydrogenated products.In these greases, preferably wherein constitute the high high oleic-acid vegetables oil of ratio of the unsaturated fatty acids (particularly oleic acid) in the lipid acid of ester, like rapeseed oil, sunflower oil and VT 18, the more preferably high oleic acid grease that further improves of oleic acid ratio.
The base oil of flame retardant resistance hydraulic fluid compositions of the present invention can be to be selected from one or more of the group be made up of above-mentioned synthetic ester and grease.
In above-mentioned synthetic ester and/or grease, the ratio of unsaturated fatty acids must be 20 moles more than the % in constituting the lipid acid of ester, preferred 50 moles more than the %, and more preferably 70 moles more than the %.If the ratio of unsaturated fatty acids is 20 moles more than the %; The lipid acid that then constitutes can be selected from sfas, unsaturated fatty acids, straight chain fatty acid and branched chain fatty acid, but promptly preferably comprises more a large amount of unsaturated fatty acidss for the effect by the amine antioxidants of two (4-dialkylamino phenyl) methane of formula (1) expression in view of component (C).
If the ratio of unsaturated fatty acids is lower than 20 moles of % in the lipid acid of formation ester; Then blend components (C) is suppressing viscosity and acid number effective aspect the starting stage increase of hydraulicefficiency oil use; But use further carry out after, the deterioration product is tending towards becoming sludge rapidly and in hydraulicefficiency system, having problems.
In order further to improve the effect that suppresses the zinc stripping, the acid number of ester must be below the 1.0mgKOH/g.If ester has the acid number greater than 1.0mgKOH/g; Then its constituents for suppressing (B) is that metal corrosion inhibitor (it is the alkyl thiadiazoles) and component (D) are the effect of nitrogen based metal deactivators (it is triazole compounds); And with the promotes oxidn deterioration, thereby composite inhibiting prevent the zinc stripping property.
To the not special restriction of the kinematic viscosity of these base oils.Yet, the preferred 10-200mm of kinematic viscosity under 40 ℃ 2/ s, more preferably 15-150mm 2/ s, more preferably 20-100mm 2/ s, this is because the flame retardant resistance of gained hydraulic composition, attrition resistance and anti-burn property (anti-seizure properties) are excellent and less through the power loss that stirs resistance.To the also not special restriction of the viscosity index of base oil.Yet in order at high temperature to keep the purpose of oil film, viscosity index is preferred more than 80, more preferably more than 100.In addition, pour point is also chosen wantonly, but during the winter viewpoint of the startability of pump, preferred below-5 ℃, more preferably-15 ℃ below.
Flame retardant resistance hydraulic fluid compositions of the present invention comprises the alkyl thiadiazoles, and promptly metal corrosion inhibitor is as component (B).
The alkyl thiadiazoles is preferably by 1,3 of following formula (2) expression, 4-thiadiazoles, by 1,2 of following formula (3) expression, 4-thiadiazoles or by 1,4 of following formula (4) expression, 5-thiadiazoles.Selectively, preferably use their two or more mixture.
Figure BDA00001875862200101
R wherein 5And R 6Can be same to each other or different to each other, and independently of one another for hydrogen or have the alkyl of 1-20 carbon atom, and a and b can be same to each other or different to each other, and be the integer of 0-8 independently of one another.
Figure BDA00001875862200102
R wherein 7And R 8Can be same to each other or different to each other, and independently of one another for hydrogen or have the alkyl of 1-20 carbon atom, and c and d can be same to each other or different to each other, and be the integer of 0-8 independently of one another.
Figure BDA00001875862200103
R wherein 9And R 10Can be same to each other or different to each other, and independently of one another for hydrogen or have the alkyl of 1-20 carbon atom, and e and f can be same to each other or different to each other, and be the integer of 0-8 independently of one another.
The specific examples of this type of thiadiazole compound comprises 2, two (the n-hexyl dithio)-1,3 of 5-, 4-thiadiazoles, 2, two (the n-octyl dithio)-1,3 of 5-, 4-thiadiazoles, 2, two (the 2-ethylhexyl dithio)-1 of 5-; 3,4-thiadiazoles, 2, two (the n-nonyl dithio)-1,3 of 5-, 4-thiadiazoles, 2,5-two (1,1; 3,3-tetramethyl butyl dithio)-1,3,4-thiadiazoles, 3, two (the n-hexyl dithio)-1,2 of 5-, 4-thiadiazoles, 3; Two (the n-octyl dithio)-1,2 of 5-, 4-thiadiazoles, 3, two (the n-nonyl dithio)-1,2 of 5-, 4-thiadiazoles, 3,5-two (1; 1,3,3-tetramethyl butyl dithio)-1,2,4-thiadiazoles, 4, two (the n-hexyl dithio)-1,2 of 5-; 3-thiadiazoles, 4, two (the n-octyl dithio)-1,2 of 5-, 3-thiadiazoles, 4, two (the n-nonyl dithio)-1,2 of 5-, 3-thiadiazoles and 4; Two (1,1,3,3-tetramethyl butyl dithio)-1,2 of 5-, the 3-thiadiazoles, with and composition thereof.
Flame retardant resistance hydraulic fluid compositions of the present invention is with more than the 0.001 quality %, and more than the preferred 0.005 quality %, more preferably the above amount of 0.01 quality % comprises the alkyl thiadiazoles as component (B), based on the compsn total mass.Less than 0.001 quality %, then the gained oil compsns can not obtain to prevent the zinc stripping property like the content of fruit component (B).Flame retardant resistance hydraulic fluid compositions of the present invention is with below the 1.0 quality %, and below the preferred 0.8 quality %, more preferably the amount below the 0.6 quality % comprises component (B), based on the compsn total mass.Greater than 1.0 quality %, then the gained oil compsns is probably owing to the decomposition of alkyl thiadiazoles becomes sludge like the content of fruit component (B).
Flame retardant resistance hydraulic fluid compositions of the present invention can contain two (the 4-dialkylamino phenyl) methane by formula (1) expression, and it is that amine antioxidants is as component (C).
Figure BDA00001875862200111
In the formula (1), R 1, R 2, R 3And R 4Can be same to each other or different to each other, and independently of one another for having the straight or branched alkyl of 1-6 carbon atom.If any R 1, R 2, R 3And R 4The carbon number of group is greater than 6, and then the ratio of functional group can be little in the molecule, might cause the disadvantageous effect to antioxidant effect.By R 1, R 2, R 3And R 4The instance of the alkyl of expression comprises methyl, ethyl, propyl group, butyl, amyl group and hexyl (all alkyl are straight or branched).
In amine antioxidants by formula (1) expression, preferred R wherein 1, R 2, R 3And R 4Independently of one another for methyl, ethyl or have those of branched-chain alkyl of 3 or 4 carbon atoms, R wherein most preferably 1, R 2, R 3And R 4Be those of methyl or ethyl independently of one another.
Flame retardant resistance hydraulic fluid compositions of the present invention is with below the preferred 5.0 quality %, and more preferably below the 3.0 quality %, more preferably the amount below the 1.0 quality % is included as the component (C) of two (4-dialkylamino phenyl) methane, based on the compsn total mass.Content greater than 5.0 quality % is not preferred, and this is because it causes the formation of sludge.
Otherwise oil compsns is with more than the 0.001 quality %, and more preferably more than the 0.005 quality %, more preferably the above amount of 0.01 quality % comprises component (C), based on the compsn total mass.Content less than 0.001 quality % is not preferred, and this is because resulting composition can not suppress the oxidative degradation of ester fully thereby can not suppress the zinc stripping.
Flame retardant resistance hydraulic fluid compositions of the present invention can be included as the triazole compounds of nitrogen based metal deactivators as component (D).For the component (D) of triazole compounds is preferably selected from the group of being made up of triazole derivative, OR 10154 and tolytriazole verivate.The specific examples of OR 10154 comprises N, two (2-the ethylhexyl)-4-methyl isophthalic acid H-benzotriazoles of N--1-methylamine and N, two (2-the ethylhexyl)-5-methyl isophthalic acid H-benzotriazoles of N--1-methylamine.
The flame retardant resistance hydraulic fluid compositions is with more than the preferred 0.0001 quality %, and more preferably more than the 0.0005 quality %, more preferably the above amount of 0.001 quality % comprises component (D), based on the compsn total mass.Content less than 0.0001 quality % is not preferred, and this is because resulting composition can not fully suppress the zinc stripping.Otherwise oil compsns is with below the 1.0 quality %, and more preferably below the 0.8 quality %, more preferably the amount below the 0.5 quality % comprises component (D), based on the compsn total mass.Content greater than 1.0 quality % is not preferred, because component (D) is difficult to be dissolved in the ester base oil, thereby becomes sludge owing to the deterioration of additive probably.
Flame retardant resistance hydraulic fluid compositions of the present invention can contain as being selected from (E1) sulfur-bearing SULPHOSUCCINIC ACID ESTER, (E2) acid phosphoric acid ester, (E3) acid phosphate amine salt and (E4) at least a abrasion resisting components of additives (E) of phosphorous acid ester, with the performance of further raising compsn.
(E1) specific examples of sulfur-bearing SULPHOSUCCINIC ACID ESTER comprises that its alkyl has the tri o cresyl thiophosphate alkyl ester of 4-18 carbon atom; Tri o cresyl thiophosphate oil base ester; Triphenyl-thiophosphate; Thiophosphoric acid trimethylbenzene ester; Tri o cresyl thiophosphate (YLENE) ester; Thiophosphoric acid tolyl diphenyl ester; Thiophosphoric acid YLENE diphenyl ester (xylenyldiphenyl phosphorothionate); Tri o cresyl thiophosphate (n-propyl phenyl) ester; Tri o cresyl thiophosphate (isopropyl phenyl) ester; Tri o cresyl thiophosphate (n-butylphenyl) ester; Tri o cresyl thiophosphate (isobutyl phenenyl) ester; Tri o cresyl thiophosphate (secondary butyl phenenyl) ester and tri o cresyl thiophosphate (tert-butyl-phenyl) ester.
(E2) specific examples of acid phosphoric acid ester comprises that its alkyl has dialkyl group acid phosphoric acid ester and two oil base acid phosphoric acid esters (dioleyl acid phosphates) that the alkyl acid SULPHOSUCCINIC ACID ESTER of 7-18 carbon atom, its alkyl have 6-18 carbon atom.
(E3) specific examples of acid phosphorous acid ester amine salt comprises the salt of aforementioned acid phosphorous acid ester and following amine: the amine of the alkyl that said amine is amine with alkyl of 1-8 carbon atom, have two 1-8 carbon atoms and have the amine of the alkyl of three 1-8 carbon atoms.
(E4) specific examples of phosphorous acid ester comprises dialkyl phosphite, phosphorous acid two oil base esters, phosphorous acid diphenyl ester, phosphorous acid diformazan phenyl ester, the trialkyl phosphite with alkyl of three 4-12 carbon atoms, tricresyl phosphite oil base ester, triphenyl phosphite and the tricresyl phosphite of the alkyl with two 4-12 carbon atoms.
Component (E) is preferably any (E1) sulfur-bearing phosphorous acid ester, (E2) acid phosphorous acid ester, (E3) acid phosphorous acid ester amine salt, and this is because them and the good effect of synthetic ester or grease base oil combination demonstration.
When flame retardant resistance hydraulic fluid compositions of the present invention and component (E) blend, its content is preferably below the 5 quality %, more preferably 2 quality %, and more preferably 1.5 quality % are based on the compsn total mass.Content greater than 5 quality % is not preferred, and this is because the thermostability of resulting composition can be poor, thereby causes that sludge forms.Otherwise the content of component (E) is preferably more than the 0.001 quality %, more preferably more than the 0.005 quality %, more preferably more than the 0.01 quality %, based on the compsn total mass.Content less than 0.001 quality % is not preferred, and this is because can not expect the attrition resistance of resulting composition and the improvement of anti-burn property.
The use of phenol antioxidant can be given good oxidation-resistance and sludge inhibition to flame retardant resistance hydraulic fluid compositions.To the not special restriction of phenol antioxidant, this is because can use as any alkylphenol compounds of lubricant with inhibitor.Yet the preferred Hinered phenols of phenol antioxidant such as alkylphenol and bis-phenol comprise those of thioether (sulfide) group and ester bond in the preferred molecule.
Flame retardant resistance hydraulic fluid compositions of the present invention is with below the preferred 5 quality %, more preferably 2 quality %, and more preferably the amount of 1.5 quality % comprises phenol antioxidant, based on the compsn total mass.Content greater than 5 quality % is not preferred, and this is because it causes that sludge forms.Otherwise oil compsns is with more than the preferred 0.01 quality %, and more than the 0.05 quality %, more preferably the above amount of 0.1 quality % comprises phenol antioxidant, based on the compsn total mass.Content less than 0.01 quality % neither be preferred, and this is because the antioxidant effect of resulting composition can be insufficient.
As stated; Among the present invention; Be selected from synthetic ester and greasy at least a base oil only with component (B) with further be selected from more than one additive and phenol antioxidant blend, production oxidation-resistance thus and attrition resistance excellent flame hydraulic fluid compositions by component (C), (D) and the group (E) formed.Yet; If necessary; In order further to improve these performances, said oil compsns can with other inhibitor except above-mentioned inhibitor, rust-preventive agent, except above-mentioned metal passivator other metal passivator, except above-mentioned abrasion resisting agent other abrasion resisting agent, viscosity index improver, pour point reducer, skimmer, emulsion splitter, prevent any or suitable combination blend of the various additives of demulcent and oiliness improver.
Except component (C), can also make up and use other amine antioxidants as amine antioxidants.The representative instance of amine antioxidants comprises by the PA of formula (5) expression and the p that is represented by formula (6), p '-dialkyl diphenylamine.
Figure BDA00001875862200151
R wherein 11For hydrogen or have the alkyl of 1-16 carbon atom.
Figure BDA00001875862200152
R wherein 12And R 13Independently of one another for having the straight or branched alkyl of 1-16 carbon atom.
The content of other amine antioxidants except that component (C) is preferably 0.001-2.0 quality %, based on the compsn total mass.
The specific examples of rust-preventive agent comprises amino acid derivative; The partial ester of polyvalent alcohol; Ester such as lanolin fatty acid ester, alkyl succinic acid ester and alkenyl succinic acid ester; Sarkosine; Polyol partial esters such as sorbitan fatty acid esters; Metallic soap such as fatty acid metal salt, lanolin fatty acid metal-salt and oxidized petroleum waves metal-salt; Sulphonate such as calcium sulphonate and barium sulfonate; Oxidized petroleum waves; Amine; Phosphoric acid; And phosphoric acid salt.In these rust-preventive agent, preferably use amino acid derivative, this is because their good rust-proof effects.
The instance of above-mentioned amino acid derivative comprises the compound by following formula (7) expression:
Figure BDA00001875862200161
In following formula (7), A is the group by formula (8) or (9) expression, and B has the alkyl of 1-12 carbon atom or the residue of the monocarboxylic ester represented by following formula (10), R 14For having the alkyl of 4-12 carbon atom, and R 15For having the alkyl of 1-10 carbon atom:
R 17O-CO-R 16-(8)
R 19O-CO-R 18-CO-(9)
-C-CO-O-R 20(10)
Wherein, R 16For having the alkylidene group of 1-12 carbon atom, R 18For having the alkylidene group of 1-10 carbon atom, R 17And R 19Be hydrogen or alkyl independently of one another with 1-10 carbon atom, and R 20For having the alkyl of 1-10 carbon atom.
Among the present invention, hydraulic fluid compositions can have any one or more compound that is selected from these rust-preventive agent with any amount blend.Yet the preferred 0.001-2.0 quality of its content % usually is based on the total mass of compsn.
The specific examples of other metal passivator except component (D) comprises glyoxaline compound.In the present invention, hydraulic fluid compositions can have any one or more compound that is selected from these metal passivators with any amount blend.Yet its content is preferably 0.0001-1 quality % usually, based on the total mass of compsn.
The specific examples of viscosity index improver comprises overstepping one's bounds powder class viscosity index improver, is selected from the monomeric multipolymer of various methacrylic esters or its hydrogenated compound, ethene-alpha-olefin copolymer (terminal olefin can be propylene, 1-butylene or 1-amylene) or its hydrogenated compound, polyisobutene or its hydrogenated compound like one or more; The hydrogenated compound of vinylbenzene-diene and polyoxyethylene alkylphenyl ethene.In the present invention, hydraulic fluid compositions can have any one or more of these viscosity index improvers with any amount blend.Yet its content is preferably 0.01-10 quality % usually, based on the total mass of compsn.
The specific examples of pour point reducer comprises that one or more are selected from the monomeric multipolymer of various propenoate and methacrylic ester or its hydrogenated compound.In the present invention, hydraulic fluid compositions can have any one or more of these pour point reducers with any amount blend.Yet its content is preferably 0.01-5 quality % usually, based on the total mass of compsn.
The specific examples of skimmer comprises silicone such as SE30 and fluorosilicone.In the present invention, hydraulic fluid compositions can have any one or more of these skimmers with any amount blend.Yet its content is preferably 0.001-0.05 quality % usually, based on the total mass of compsn.
The instance of emulsion splitter comprises polyether polyols, polyoxyalkylene alkyl ether, polyoxy alkylidene alkylamide and polyoxy alkylidene fatty ester etc.
The specific examples of anti-demulcent comprises polyol ester (full ester and partial ester).
The specific examples of oiliness improver comprises lipid acid, ester and alcohol.Usually, its content is preferably 0.01-0.5 quality %, based on the total mass of hydraulic fluid compositions.
Embodiment
To describe the present invention in more detail with reference to following examples and comparative example, but the invention is not restricted to this.Measure and carry out the flash-point and the various test of each compsn according to following method.
[flash-point]
The flash-point of each compsn is measured according to JIS J 2265 " crude oil and petroleum products-flashing test (Cleveland opening agar diffusion method) ".
[four-ball test]
According to ASTM D 2783-88 " the lubricating fluid extreme pressure property is measured with standard test methods (four ball methods) ", be 1200min at revolution -1, load is to carry out this test 1 hour under 75 ℃ for 294N, oily temperature, thereby the MV of polishing scratch (scar) diameter (mm) of measurement fixed three balls.
[test of FZG gear]
Carry out this test according to ASTM D 5182.This test is 1500min at revolution -1Down with in oily temperature is to begin under 90 ℃, and makes the gear load drive 15 minutes simultaneously through the specified weight that applies regulation in each stage.Estimate the anti-burn property of each oil in the stage that burn takes place.The load stage of gear burn is defined as defective.
[wing pump test]
Carry out wing pump test 100 hours according to ASTM D 2882.In the weight of test fore-and-aft survey impeller and ring, thereby measure wear loss (mg).
[dry type TOST test]
" the TOST oxidation stability test " of regulation carries out among this experimental evidence JIS K 2514.Through 300mL sample oil being put into the container of regulation, then coil shape iron and copper catalyst to be put into wherein, oxidation stability test was carried out in the water-bath of then this container being put under the temperature that remains on 95 ℃ in 20 days.Do not make water.At duration of test, bit by bit taking out sample oil increases (mgKOH/g) and sludge amount (mg/50mL) (wherein the sample oil of specified quantitative filters with strainer, and the weight of resistates is scaled the amount of every 50mL) to measure acid number.
[zinc dissolution test]
The JIS B 2301-1976 that puts into the beaker that comprises 200mL sample oil according to screw-type (screwed type) the malleable iron pipe fitting of one of them regulation is to carry out dip test under 120 ℃ 20 days in temperature.After the test, the zinc amount (quality ppm) of stripping in the measure sample oil is to compare the zinc stripping property of each sample oil.
Used component is following in embodiment and the comparative example.
(A) base oil
A1: the ester (kinematic viscosity under 40 ℃: 47.2mm of the mixed fatty acid of TriMethylolPropane(TMP) and oleic acid, sad and capric acid 2/ s, viscosity index: 180, percent unsaturation: 70 moles of %, acid number: 0.5)
A2: the ester (kinematic viscosity under 40 ℃: 45.2mm of the mixed fatty acid of TriMethylolPropane(TMP) and oleic acid, sad and capric acid 2/ s, viscosity index: 185, percent unsaturation: 90 moles of %, acid number: 2.0)
A3: the ester (kinematic viscosity under 40 ℃: 34.2mm of the mixed fatty acid of TriMethylolPropane(TMP) and oleic acid, sad and capric acid 2/ s, viscosity index: 130, percent unsaturation: 10 moles of %, acid number: 0.3)
A4: the ester (kinematic viscosity under 40 ℃: 66.2mm of the mixed fatty acid of tetramethylolmethane and oleic acid, sad and capric acid 2/ s, viscosity index: 160, percent unsaturation: 70 moles of %, acid number: 1.0)
(B) metal passivator
B1:2, two (the 2-ethylhexyl dithio)-1,3 of 5-, 4-thiadiazoles
B2:2, two (the n-hexyl dithio)-1,3 of 5-, 4-thiadiazoles
(C) inhibitor
C1: two (4-dimethylaminophenyl) methane
C2: alpha-naphthylamine
C3:4,4 '-methylene-bis (2,6 di t butyl phenol)
(D) nitrogen based metal deactivators
D1:N, two (2-the ethylhexyl)-4-methyl isophthalic acid H-benzotriazoles of N--1-methylamine
D2: benzotriazole
(E) abrasion resisting agent
E1:2-ethylhexyl acid phosphoric acid ester
E2: Tritolyl Phosphate
(F) other additive
E3: dehydrated sorbitol mono-fatty acid ester
With 2 said, use wherein that the ratio of unsaturated fatty acids is the comparative example 4 of the base oil of 10 moles of % in the lipid acid that constitutes ester like table 1,, compare with embodiment 6 although its acid number is low, poorer aspect oxidative stability, particularly form more sludge.
Use the comparative example 1-3 of its acid number as the base oil A2 of 2.0mgKOH/g, although the ratio of unsaturated fatty acids is 90 moles of % (these are high) in the lipid acid that constitutes ester, compare with 5 with embodiment 2, its zinc stripping quantity is bigger.
Table 1
Figure BDA00001875862200211
Table 2
Figure BDA00001875862200221
Utilizability on the industry
Flame retardant resistance hydraulic fluid compositions of the present invention is suitable in the application with use under the high high-temperature and high-pressure conditions of fire occurrence risk property most; As be used for the application of aluminum dipping form casting forcing machine or the operation of iron work equipment; And it is applicable to HPP; Attrition resistance, sludge inhibition and particularly zinc stripping inhibition are excellent, make to use for a long time.Thereby said composition is significantly useful in industry.

Claims (3)

1. flame retardant resistance hydraulic fluid compositions, it comprises:
(A) be selected from least a base oil of the group of forming by synthetic ester and grease, said synthetic ester and grease in the lipid acid of formation ester, comprise 20 moles more than the % unsaturated fatty acids and have acid number be below the 1.0mgKOH/g and
(B) the alkyl thiadiazoles of the amount of 0.001-1.0 quality % is based on the compsn total mass.
2. flame retardant resistance hydraulic fluid compositions according to claim 1, it further comprises:
(C) two (4-dialkylamino phenyl) methane of the amount of 0.001-5.0 quality % by following formula (1) expression, based on the compsn total mass:
Figure FDA00001875862100011
R wherein 1, R 2, R 3And R 4Be same to each other or different to each other, and independently of one another for having the alkyl of 1-6 carbon atom.
3. flame retardant resistance hydraulic fluid compositions according to claim 1 and 2, it further comprises:
(D) at least a triazole compounds that is selected from the group of being made up of triazole derivative, OR 10154 and tolytriazole verivate of the amount of 0.0001-1.0 quality % is based on the compsn total mass.
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CN103224828A (en) * 2013-04-09 2013-07-31 天津市联瑞阻燃材料有限公司 Aircraft-grade high-pressure anti-combustible oil with base oil of tricresyl phosphate and production method thereof
CN103224829A (en) * 2013-04-09 2013-07-31 天津市联瑞阻燃材料有限公司 Special cleaning fire-resistant oil and preparation method thereof
CN103224827A (en) * 2013-04-09 2013-07-31 天津市联瑞阻燃材料有限公司 High-pressure anti-combustible oil with base oil of tricresyl phosphate and production method thereof
CN104140862A (en) * 2014-07-10 2014-11-12 新乡市恒星化工有限责任公司 Compound extreme pressure lithium-based lubricating grease additive and preparation method thereof
CN104342268A (en) * 2014-10-08 2015-02-11 无锡阳工机械制造有限公司 Fire resistant hydraulic oil and preparation method thereof
CN108277068A (en) * 2018-03-16 2018-07-13 纳拓润滑技术江苏有限公司 A kind of biodegradable fire resistant hydraulic fluid
CN111848919A (en) * 2020-08-07 2020-10-30 宁波耀众模塑科技有限公司 Flame retardant for polyurethane foaming product
CN114181757A (en) * 2020-09-14 2022-03-15 安美科技股份有限公司 Phosphate fire-resistant oil

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CN103224826A (en) * 2013-04-09 2013-07-31 天津市联瑞阻燃材料有限公司 High-pressure anti-combustible oil with base oil of trixylenyl phosphate and production method thereof
CN103224828A (en) * 2013-04-09 2013-07-31 天津市联瑞阻燃材料有限公司 Aircraft-grade high-pressure anti-combustible oil with base oil of tricresyl phosphate and production method thereof
CN103224829A (en) * 2013-04-09 2013-07-31 天津市联瑞阻燃材料有限公司 Special cleaning fire-resistant oil and preparation method thereof
CN103224827A (en) * 2013-04-09 2013-07-31 天津市联瑞阻燃材料有限公司 High-pressure anti-combustible oil with base oil of tricresyl phosphate and production method thereof
CN103224829B (en) * 2013-04-09 2014-06-04 天津市联瑞阻燃材料有限公司 Special cleaning fire-resistant oil and preparation method thereof
CN104140862A (en) * 2014-07-10 2014-11-12 新乡市恒星化工有限责任公司 Compound extreme pressure lithium-based lubricating grease additive and preparation method thereof
CN104140862B (en) * 2014-07-10 2016-03-30 新乡市恒星科技有限责任公司 A kind of extreme pressure compound lithium base grease additive and preparation method thereof
CN104342268A (en) * 2014-10-08 2015-02-11 无锡阳工机械制造有限公司 Fire resistant hydraulic oil and preparation method thereof
CN108277068A (en) * 2018-03-16 2018-07-13 纳拓润滑技术江苏有限公司 A kind of biodegradable fire resistant hydraulic fluid
CN111848919A (en) * 2020-08-07 2020-10-30 宁波耀众模塑科技有限公司 Flame retardant for polyurethane foaming product
CN114181757A (en) * 2020-09-14 2022-03-15 安美科技股份有限公司 Phosphate fire-resistant oil
CN114181757B (en) * 2020-09-14 2022-06-28 安美科技股份有限公司 Phosphate fire-resistant oil

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